JP2019151808A - Conjugated diene-based polymer composition, and tire - Google Patents

Abstract

To provide a conjugated diene-based polymer composition excellent in balance of rolling resistance and wet grip property at high level, and excellent in scorch resistance and operation stability.SOLUTION: There is provided a conjugated diene-based polymer composition containing a rubber component containing a conjugated diene polymer (a), a silica-based inorganic filler (b), a hydrogenated copolymer (c), the hydrogenated copolymer (c) has a polymer block (A) consisting of a vinyl aromatic monomer unit, and a hydrogenated copolymer block (B) consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit, and having properties (1) and (2). (1) Hydrogenation rate of a double bond of the conjugated diene monomer unit is 75% or more. (2) One peak of loss tangent (tanδ) in a kinetic viscoelastic spectrum of the hydrogenated copolymer (c) exists only in a range of a crystallization peak temperature due to the conjugated diene-based polymer (a) by differential scanning calorimetry (DSC) or higher and less than -10°C.SELECTED DRAWING: None

Description

  The present invention relates to a conjugated diene polymer composition and a tire.

In recent years, with the emphasis on resource saving and environmental measures, the level of demand for automobile tires with excellent fuel efficiency is increasing.
As a method of manufacturing tires with excellent fuel efficiency, the tread is composed of two layers, a cap tread on the ground contact side and a base tread on the opposite side, and the tread is made of a material that reduces rolling resistance. Therefore, a method is known that uses a rubber material that can suppress the energy loss of the tire and can form a crosslinked rubber that is excellent in rolling resistance characteristics.
As described above, in view of the growing demand for low fuel consumption for tires, there is a technology for improving the rolling resistance characteristics of the rubber material that constitutes the tread in order to obtain a tire with even better fuel efficiency. It is being considered.

  As a method of improving the fuel efficiency of the rubber composition, for example, a method of reducing the blending amount of an inorganic filler such as silica is known, but the hardness of the rubber composition is lowered and the wet grip performance is deteriorated. There is a tendency to do. Therefore, a method for improving both fuel efficiency and wet grip in a balanced manner is desired.

In order to improve characteristics such as wet grip properties, a method of blending a resin (resin) such as an indene resin, a terpene resin, an alkylphenol resin, a rosin derivative, or a maleic acid resin has been proposed.
On the other hand, Patent Documents 1 and 2 disclose rubber compositions in which a hydrogenated block copolymer is blended with a rubber component such as a styrene-butadiene random copolymer.

JP-A-1-182333 Special table 2014-520017 gazette

  However, studies on the improvement of fuel efficiency and wet grip properties are progressing with a focus on the structure of conjugated diene polymers, but the conventionally proposed technology is based on the scorch resistance and handling stability of resin compositions. There is still a problem that there is still room for improvement in terms of improving the performance.

  Then, in view of the problem which the prior art mentioned above has in this invention, it aims at providing the modified conjugated diene type polymer composition excellent in scorch resistance and steering stability.

As a result of intensive research in order to solve the above-described problems of the prior art, the present inventors have included a specific amount of a specific polymer component in a rubber component containing a conjugated diene polymer, thereby providing rolling resistance characteristics. The inventors have found that the scorch resistance is improved without deteriorating the wet grip property and the handling stability, and have completed the present invention.
That is, the present invention is as follows.

[1]
A rubber component containing a conjugated diene polymer (I);
Silica-based inorganic filler (b),
A hydrogenated copolymer (c),
Is a conjugated diene polymer composition containing
The hydrogenated copolymer (c) is a hydrogenated non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit.
At least obtained by hydrogenating a polymer block (A) comprising a vinyl aromatic monomer unit and a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit. Having one hydrogenated copolymer block (B),
Having polymer blocks (A) at both ends;
And it is a hydrogenated copolymer having the following characteristics (1) and (2):
Conjugated diene polymer composition.
(1) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more.
(2) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c), the peak of loss tangent (tan δ) is attributed to the conjugated diene polymer (A) by differential scanning calorimetry (DSC). One exists only in the range from the crystallization peak temperature to below -10 ° C.
[2]
The conjugated diene polymer composition according to [1] above, wherein a vinyl bond amount of the non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit is less than 40%. object.
[3]
The conjugated diene polymer composition according to [1] or [2] above, wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is 40 to 60% by mass.
[4]
Any of [1] to [3] above, wherein the content of the polymer block (A) composed of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is 0 to 60% by mass. The conjugated diene polymer composition according to any one of the above.
[5]
The conjugated diene polymer composition according to any one of [1] to [4], further including carbon black.
[6]
The conjugated diene polymer composition according to any one of [1] to [5], which is used for a base tread.
[7]
A tire comprising a tread including a crosslinked product of the conjugated diene polymer composition according to any one of [1] to [6].

  According to the present invention, a conjugated diene polymer composition having a high balance between rolling resistance characteristics and wet grip properties, excellent scorch resistance, and handling stability can be obtained.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail below. In addition, the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with various modifications within the scope of the gist.

(Conjugated diene polymer composition)
The conjugated diene polymer composition of this embodiment is
A rubber component containing a conjugated diene polymer (I);
Silica-based inorganic filler (b),
A hydrogenated copolymer (c),
Is a conjugated diene polymer composition.
The hydrogenated copolymer (c) is a hydrogenated non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit.
At least obtained by hydrogenating a polymer block (A) comprising a vinyl aromatic monomer unit and a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit. One hydrogenated copolymer block (B),
It is a hydrogenated copolymer having a polymer block (A) at both ends and having the following characteristics (1) and (2).
(1) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more,
(2) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c), the peak of loss tangent (tan δ) is attributed to the conjugated diene polymer (A) by differential scanning calorimetry (DSC). One exists only in the range from the crystallization peak temperature to less than -10 ° C.

(Rubber component)
The conjugated diene polymer composition of this embodiment contains a rubber component, and the rubber component contains a conjugated diene polymer (A).

(Conjugated diene polymer (I))
From the viewpoint of improving the scorch resistance of the conjugated diene polymer composition, the conjugated diene polymer (A) may be either not modified or modified. When the conjugated diene polymer composition is used for tire tread applications, it is blended into the tire by appropriately selecting a modified conjugated diene copolymer (a) (introduced with a functional group). It is possible to improve the affinity between the filler such as silica and the copolymer, and improve tire performance such as low fuel consumption and wet grip. Depending on the type of resin added in the step of preparing the conjugated diene polymer composition, tire performance such as low fuel consumption and wet grip properties may be deteriorated, but it contains a hydrogenated copolymer (c) described later. By doing so, the conjugated diene polymer composition of the present embodiment tends to maintain these performances. Therefore, the conjugated diene polymer composition of the present embodiment is more suitable for tire applications by selecting a conjugated diene polymer (A) that is excellent in fuel economy and / or wet grip properties. It is possible to make a simple composition.
Examples of the modified conjugated diene polymer (a) (referred to as a modified conjugated diene copolymer) include those having an adsorptivity to a silica column, such as a silica column. Examples of the modified conjugated diene polymer having the above adsorptivity include a modified conjugated diene polymer having a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent.

In this specification, the “silica-based column” means a column packed with porous silica gel having a diameter of several μm to several tens of μm, and other than the organic solvent-based GPC column used in Examples described later. Including water / organic solvent based GPC columns.
In the present specification, “having adsorptivity” means that the modification rate determined by the modification rate measurement in Examples described later satisfies 5% or more.

  A modified conjugated diene polymer having a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent, for example, by polymerizing a conjugated diene compound using an anionic polymerization initiator, or A compound having a nitrogen atom in the molecule and two or more epoxy groups at the polymerization active terminal of a conjugated diene polymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound, or an intramolecular It is obtained by reacting a compound having two or more alkoxy groups having a nitrogen atom and bonded to a silyl group.

The conjugated diene compound used for constituting the conjugated diene polymer (a) is not limited to the following, but for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 -Butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned.
Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability.
These may be used alone or in combination of two or more. In particular, 1,3-butadiene is preferable.

The conjugated diene polymer (A) may use an aromatic vinyl compound as a monomer.
The aromatic vinyl compound is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinyl Xylene, vinyl naphthalene, diphenylethylene and the like can be mentioned.
Among these, styrene is preferable from the viewpoint of industrial availability. An aromatic vinyl compound is not limited to what consists only of 1 type, You may use 2 or more types together.

The conjugated diene polymer (A) may be a random copolymer.
Examples of the random copolymer include, but are not limited to, for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-isoprene-styrene random copolymer. A polymer etc. are mentioned.
The composition distribution of each monomer in the copolymer chain is not limited to the following, but for example, a completely random copolymer close to a statistical random composition, the composition is distributed in a tapered shape. Examples thereof include a tapered (gradient) random copolymer.
The bonding mode of the conjugated diene, that is, the composition of 1,4-bonds, 1,2-bonds, etc. may be uniform or distributed.

The amount of the conjugated diene in the conjugated diene polymer (I) is not particularly limited, but is preferably 50 to 100% by mass, for example, 60 to 80% by mass when used for a tire tread application. It is more preferable.
Moreover, the amount of bonded aromatic vinyl in the conjugated diene polymer (A) is not particularly limited, but is preferably 0 to 50% by mass, and more preferably 20 to 40% by mass. When the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate having an excellent balance between low hysteresis loss and wet skid resistance and excellent wear resistance can be obtained.
Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it can measure by the method according to the Example mentioned later.

Moreover, the amount of vinyl bonds in the conjugated diene bond unit of the conjugated diene polymer (A) is not particularly limited, but is preferably 10 to 75 mol%, and more preferably 25 to 65 mol%.
When the vinyl bond content of the conjugated diene polymer (A) is in the above range, a vulcanizate having an excellent balance between low hysteresis loss and wet skid resistance and satisfying wear resistance can be obtained.
Here, when the conjugated diene polymer (a) is a copolymer of butadiene and styrene, a butadiene bond unit is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond content (1,2-bond content) can be determined.

Low hysteresis when the microstructure (the amount of each bond in the conjugated diene polymer (A)) is in the above range and the glass transition temperature of the conjugated diene polymer is in the range of −45 to −15 ° C. A more excellent vulcanizate can be obtained due to the balance between loss and wet skid resistance.
Regarding the glass transition temperature, in accordance with ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature.

When the conjugated diene polymer (A) is a conjugated diene-aromatic vinyl copolymer, it is preferable that the number of blocks in which 30 or more aromatic vinyl units are linked is small or absent.
Specifically, when the conjugated diene polymer (a) is a butadiene-styrene copolymer, the method described in Kolthoff's method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In the known method of decomposing a polymer by the method described in the above and analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are linked is preferably 5 masses relative to the total amount of the polymer. % Or less, more preferably 3% by mass or less.

(Method for producing conjugated diene polymer (a))
The method for producing the conjugated diene polymer (a) is described below.
<Polymerization process>
The conjugated diene polymer (A) contained in the conjugated diene polymer composition of the present embodiment has a molecular structure branched from a nitrogen-containing epoxy substituent or from a nitrogen-containing alkoxysilane substituent. A modified conjugated diene polymer having a branched molecular structure is preferred, and in the method for producing such a modified conjugated diene polymer, examples of the polymerization initiator include a polyfunctional anionic polymerization initiator and a monofunctional anion. It is preferable to carry out the polymerization step using a polymerization initiator.

[(A) Method for Producing Conjugated Diene Polymer Having Active End when Using Polyfunctional Anionic Polymerization Initiator]
First, a polyfunctional anionic polymerization initiator used in the step of polymerizing a conjugated diene polymer, which is a step before modification with an alkoxylane compound (modifier) described later on the polymerization active terminal of the conjugated diene polymer will be described. .
The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer can be prepared by reacting a polyvinyl aromatic compound and an organolithium compound.
For example, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting a polyvinyl aromatic compound, an organolithium compound and a monovinyl aromatic A method of reacting a polyvinyl aromatic compound after reacting with an aromatic compound, a method of reacting an organolithium compound in the presence of two or three of a conjugated diene compound and / or a monovinyl aromatic compound and a polyvinyl aromatic compound, etc. Is mentioned.

In particular, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting the polyvinyl aromatic compound, a conjugated diene compound and a polyvinyl compound A polyfunctional anionic polymerization initiator prepared by a method of reacting a monoorganolithium compound in the presence of is preferable.
In order to promote and stabilize the formation of the polyfunctional anionic polymerization initiator, it is preferable to add a Lewis base to the system during the preparation.

The polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples thereof include o, m and p-divinylbenzene, o, m and p-diisopropenylbenzene, , 2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5, 4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene and the like can be mentioned.
These may be used alone or in combination of two or more.
In particular, divinylbenzene and diisopropenylbenzene are preferable, and a mixture of these o-, m-, and p-isomers may be used.

For the preparation of the polyfunctional anionic polymerization initiator, a conjugated diene compound and / or a monoaromatic vinyl compound may be used together with the polyvinyl aromatic compound.
Examples of the conjugated diene compound include, but are not limited to, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1, Examples include 3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable.
Examples of the monovinyl aromatic compound include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. preferable.
The conjugated diene compound and / or monoaromatic vinyl compound used for the adjustment of the polyfunctional anionic polymerization initiator has a polystyrene equivalent weight average molecular weight of 1,000 to 10,000 as measured by GPC. It is more preferable to add so that.

  The organolithium compound used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso- Monoorganolithium compounds such as propyllithium and benzyllithium, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,1-0-dilithiodecane, 1,1-dilithiophenylene, dilithio Polybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1 , 3,5-trilithio-2,4,6-triethylbenzene and other polyfunctional organic lithium Compounds, and the like. In particular, a monoorganolithium compound of n-butyllithium, sec-butyllithium, or tert-butyllithium is preferable.

  The solvent used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic carbonizations such as cyclopentane and cyclohexane. Hydrogen; aromatic hydrocarbons such as benzene, toluene, xylene and the like.

It is also effective to add a Lewis base into the system during the preparation process of the polyfunctional anionic polymerization initiator.
Examples of the Lewis base include, but are not limited to, tertiary monoamines, tertiary diamines, chain or cyclic ethers, and the like.
Examples of the tertiary monoamine include, but are not limited to, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytrimethylamine, N, Examples thereof include N-dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.
Examples of the tertiary diamine include, but are not limited to, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N , N ′, N′-tetramethylpropanediamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N Examples thereof include compounds such as' -tetramethylhexanediamine and dipiperidinoethane.
Examples of chain ethers include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.
Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxoranyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane. 2,2-bis (2-oxolanylbutane), 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, etc. The compound of this is mentioned.
Among Lewis bases, tertiary monoamines such as trimethylamine, triethylamine, tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine, and cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxasolanyl) Propane is preferred.
A Lewis base may be used individually by 1 type and may use 2 or more types together.

In addition, when a Lewis base is added when preparing a polyfunctional anionic polymerization initiator, it is preferably added within a range of 30 to 50,000 ppm with respect to the solvent used when preparing the polymerization initiator. More preferably, it is added within the range of 200 to 20,000 ppm.
In order to fully express the effect of promoting and stabilizing the reaction, it is preferably 30 ppm or more, ensuring the degree of freedom of microstructure adjustment in the subsequent polymerization step, collecting the solvent after polymerization, and polymerizing in the purification step In consideration of separation from the catalyst, it is preferably added at 50,000 ppm or less.

The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer (i) before the modification is such that the molar ratio of the polyvinyl aromatic compound to the organic lithium is polyvinyl aromatic compound / organic. It is preferable that the lithium is adjusted to be in the range of 0.01 to 1.0.
Molecules to which a functional group is added by a modification reaction of a conjugated diene polymer described later when the conjugated diene polymer (a) is a modified polymer as the amount of the polyvinyl aromatic compound used relative to the organic lithium is larger. The chain end ratio is increased, the affinity and reactivity with silica particles are improved, and the balance between low hysteresis loss and wet skid resistance in the conjugated diene polymer composition of this embodiment is good. Therefore, the wear resistance can be improved.
On the other hand, when the amount of the polyvinyl aromatic compound used is smaller than that of the organolithium compound, the processability in kneading the composition can be improved, and from this point of view, the amount is 1.0 mol or less. preferable.
In general, when the low hysteresis loss property is improved, the Mooney viscosity of the composition tends to increase and the workability tends to deteriorate, but it is practically preferable not to increase it so much from the above viewpoint.
From the viewpoint of improving these balances, the amount of the polyvinyl aromatic compound is more preferably in the range of 0.02 to 0.5 mol, and 0.02 to 0.1 mol of 1 mol of the organic lithium compound. A range is further preferred.

The temperature at which the polyfunctional anionic polymerization initiator is prepared is preferably 10 ° C. or higher from the viewpoint of production, and 140 ° C. or lower from the viewpoint of suppressing side effects due to high temperature, more preferably in the range of 35 to 110 ° C. .
The reaction time for preparing the polyfunctional anionic polymerization initiator depends on the reaction temperature, but is in the range of 5 minutes to 24 hours.

The conjugated diene polymer before modification of the conjugated diene polymer (A) is obtained by an anionic polymerization reaction using the polyfunctional anionic polymerization initiator described above.
In particular, a conjugated diene polymer having an active end obtained by a growth reaction by living anionic polymerization is more preferable. Thereby, the modified conjugated diene polymer (a) having a high modification rate can be obtained by a modification step described later.
Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. As the reactor, any of known configurations such as a tank type with a stirrer and a tube type can be used.

The polystyrene equivalent weight average molecular weight (Mw) measured by GPC of the polyfunctional anionic polymerization initiator is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 10,000. .
The conjugated diene polymer composition of the present embodiment using the conjugated diene polymer (A) obtained by using a polyfunctional anionic polymerization initiator having a molecular weight distribution in this range has a decreased Mooney viscosity, The resulting vulcanizate has an excellent balance between low hysteresis loss and wet skid resistance.
In order to obtain a modified conjugated diene polymer (a), the conjugated diene polymer before modification is obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using the polyfunctional anionic polymerization initiator described above. Can be obtained.

If allenes, acetylenes, and the like are contained as impurities in the conjugated diene compound that is a polymerization monomer of the conjugated diene polymer (A), there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

The polymerization reaction of the conjugated diene polymer (a) is preferably performed in a solvent.
Examples of the solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof.

  By subjecting allenes and acetylenes, which are impurities, to an organometallic compound before being subjected to a polymerization reaction, a polymer having a high concentration of active terminals tends to be obtained, and a high modification rate is achieved. It is preferable because of its tendency.

In the polymerization reaction of the conjugated diene polymer before the modification of the conjugated diene polymer (A), a polar compound may be added.
By adding the polar compound, the aromatic vinyl compound can be randomly copolymerized with the conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene part. It is also effective in improving the polymerization rate.
Examples of the polar compound include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2 Ethers such as -oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butyrate, sodium-t- Examples include alkali metal alkoxide compounds such as butyrate and sodium amylate; and phosphine compounds such as triphenylphosphine.
Each of these polar compounds may be used alone or in combination of two or more.
The usage-amount of a polar compound is not specifically limited, It can select according to the objective etc. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount depending on the desired vinyl bond amount as a microstructure regulator of the conjugated diene moiety of the conjugated diene polymer. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently interrupted during the copolymerization. Alternatively, a method of adding them may be used.

  The polymerization temperature in the polymerization step of the conjugated diene polymer (a) is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, it is preferably 0 ° C. or higher, and after the polymerization is completed. From the viewpoint of sufficiently ensuring the reaction amount of the modifier with respect to the active terminal, it is preferably 120 ° C. or lower.

[(B) Method for Producing Conjugated Diene Polymer Having Polymerization Active Terminal When Using Monofunctional Anionic Polymerization Initiator]
Next, a method for producing a conjugated diene polymer (A) having a polymerization active terminal when a monofunctional anionic polymerization initiator is used will be described.
As the monofunctional anionic polymerization initiator, a compound comprising a carbon-lithium bond is particularly preferable.
Examples of the compound comprising a carbon-lithium bond include, but are not limited to, for example, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium. And organic lithium compounds.
From the viewpoint of easy industrial availability and easy control of the polymerization reaction, n-butyllithium and sec-butyllithium are preferred.
These organolithium compounds may be used alone or as a mixture of two or more.

The monofunctional anionic polymerization initiator may be used in combination with another organic alkali metal compound.
Examples of other organic alkali metal compounds include, but are not limited to, organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given. Moreover, you may use together with another organometallic compound.

An organic alkaline earth metal compound can also be used as the monofunctional anionic polymerization initiator.
Examples of organic alkaline earth metal compounds include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with organic alkali metal compounds or other organic metal compounds.

The conjugated diene polymer before modification of the conjugated diene polymer (a) is produced by using the monofunctional anionic polymerization initiator, and a polymer of a conjugated diene compound or a copolymer with an aromatic vinyl compound. If it is, it will not specifically limit, However, It is preferable that it is a copolymer obtained by growing by an anionic polymerization reaction.
In particular, the conjugated diene polymer is preferably a polymer having an active end obtained by a growth reaction by living anion polymerization.
Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.
Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. As the reactor, a tank type with a stirrer, a tube type or the like is used.
Treatment of allenes and acetylenes, which are impurities, with an organometallic compound in a polymerization system before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and further has a high modification rate. Is preferable because it tends to be achieved.

The polymerization reaction of the conjugated diene polymer (a) is preferably performed in a solvent.
Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof.

  In the polymerization reaction of the conjugated diene polymer (I), a polar compound may be added. By adding the polar compound, the aromatic vinyl compound can be randomly copolymerized with the conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene part. It is also effective in improving the polymerization rate.

As a polymerization initiator used in the polymerization step of the conjugated diene polymer described above, in addition to the polymerization initiator described above, “an organolithium compound having at least one nitrogen atom in the molecule” or “at least one in the molecule” A polymerization initiator system comprising a compound having two nitrogen atoms and an organolithium compound ”can be used.
In the polymerization initiator system, an organolithium compound having at least one nitrogen atom in the molecule may be prepared in a predetermined reactor in advance, or in a reactor for performing polymerization or copolymerization described later. It may be supplied, and at the same time as or before the polymerization or copolymerization, the compound having at least one nitrogen atom in the molecule may be reacted with organolithium.
As the “compound having at least one nitrogen atom in the molecule” used in the polymerization initiator system, compounds represented by the following general formulas (1) to (3) can be used.

In formula (1), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.

In formula (2), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.
R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms. X represents a hydrogen atom, a Cl atom, a Br atom, or an I atom.

In formula (3), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₅ and R ₁₆ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R ₁₆ represent an alkyl group having 5 to 12 carbon atoms and are branched to a part thereof. You may have a structure.

In the formula (1), R ₁₀ and R ₁₁ represent, but are not limited to, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclopropyl group, a cyclohexyl group, Examples include 3-phenyl-1-propyl group, isobutyl group, decyl group, heptyl group, and phenyl group.
The compound represented by the formula (1) is not limited to the following compounds, but examples thereof include dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di-2-ethyl. Examples include hexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine.
The compound represented by the formula (1) is not limited to these compounds, and includes analogs thereof as long as the above conditions are satisfied.
The compound represented by the formula (1) includes a hysteresis loss reduction of the conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the conjugated diene polymer of the present embodiment, and a chain transfer reaction described later. From the viewpoint of control, dibutylamine and dihexylamine are preferable, and dibutylamine is more preferable.
When R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, examples of the compound represented by the formula (1) include piperidine, hexamethyleneimine, azacyclooctane, , 3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydropyridine.
The compound represented by the formula (1) is not limited to these compounds, and includes analogs thereof as long as the above conditions are satisfied.
The compound represented by the formula (1) includes a hysteresis loss reduction of the conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the conjugated diene polymer of the present embodiment, and a chain transfer reaction described later. From the viewpoint of control, piperidine, hexamethyleneimine, azacyclooctane and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, piperidine and hexamethyleneimine are more preferable, and more preferable. Is piperidine.

In the formula (2), R ₁₄ preferably represents an alkyl group having 2 to 16 carbon atoms, more preferably 3 carbon atoms, from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. Represents 10 to 10 alkyl groups.
The compound represented by the formula (2) is not limited to the following compounds. For example, 3-chloro-dimethylpropan-1-amine, 3-chloro-diethylpropan-1-amine, 3-chloro-dibutylpropane -1-amine, 3-chloro-dipropylpropan-1-amine, 3-chloro-diheptylpropan-1-amine, 3-chloro-dihexylpropan-1-amine, 3-chloropropyl-ethylhexane-1 -Amine, 3-chloro-didecylpropan-1-amine, 3-chloro-ethylpropan-1-amine, 3-chloro-ethylbutan-1-amine, 3-chloro-ethylpropan-1-amine, benzyl-3 -Chloro-ethylpropan-1-amine, 3-chloro-ethylphenethylpropan-1-amine, 3-chloro-methylphenethyl Lopan-1-amine, 1- (3-chloropropyl) piperidine, 1- (3-chloropropyl) hexamethyleneimine, 1- (3-chloropropyl) azacyclooctane, 6- (3-chloropropyl) -1 , 3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1- (3-chloropropyl) -1,2,3,6-tetrahydropyridine, 1- (3-bromopropyl) hexamethyleneimine 1- (3-iodopropyl) hexamethyleneimine, 1- (3-chlorobutyl) hexamethyleneimine, 1- (3-chloropentyl) hexamethyleneimine, 1- (3-chlorohexyl) hexamethyleneimine, 1- (3-Chlorodecyl) hexamethyleneimine.
The compound represented by the formula (2) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
The compound represented by the formula (2) includes 3-chloro-dibutylpropan-1-amine, 1- (3-chloropropyl) from the viewpoints of reactivity and interaction with inorganic fillers such as carbon and silica. ) Hexamethyleneimine is preferred, and 1- (3-chloropropyl) hexamethyleneimine is more preferred.
In the formula (2), when R ₁₄ represents a conjugated diene polymer chain having any one repeating unit of the following formulas (4) to (6), X represents a hydrogen atom.

When X in Formula (2) represents a hydrogen atom, the compound represented by Formula (2) is not limited to the following, but for example, N, N-dimethyl-2-butenyl-1-amine N, N-diethyl-2-butenyl-1-amine, N, N-dibutyl-2-butenyl-1-amine, N, N-dipropyl-2-butenyl-1-amine, N, N-diheptyl 2-butenyl-1-amine, N, N-dihexyl-2-butenyl-1-amine, N, N-dioctyl-2-butenyl-1-amine, N, N- (to di-2-ethyl Xyl) -2-butenyl-1-amine, N, N-didecyl-2-butenyl-1-amine, N, N-ethylpropyl-2-butenyl-1-amine, N, N-ethylbutyl-2-butenyl- 1-amine, N, N-ethylbenzyl-2-butenyl- -Amine, N, N-methylphenethyl-2-butenyl-1-amine, N, N-dimethyl-2-methyl-2-butenyl-1-amine, N, N-diethyl-2-methyl-2-butenyl- 1-amine, N, N-dibutyl-2-methyl-2-butenyl-1-amine, N, N-dipropyl-2-methyl-2-butenyl-1-amine, (N, N-diheptyl-2 -Methyl-2-butenyl-1-amine, N, N-dihexyl-2-methyl-2-butenyl-1-amine, N, N-dimethyl-3-methyl-2-butenyl-1-amine, N , N-diethyl-3-methyl-2-butenyl-1-amine, N, N-dibutyl-3-methyl-2-butenyl-1-amine, N, N-dipropyl-3-methyl-2-butenyl-1 -Amine, N, N-diheptyl-3-methyl- -Butenyl-1-amine, N, N-dihexyl-3-methyl-2-butenyl-1-amine, 1- (2-butenyl) piperidine, 1- (2-butenyl) hexamethyleneimine, 1- ( 2-butenyl) azacyclooctane, 6- (2-butenyl) 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1- (2-butenyl) -1,2,3,6 -Tetrahydropyridine, (2-methyl-2-butenyl) hexamethyleneimine, (3-methyl-2-butenyl) hexamethyleneimine.
The compound represented by the formula (2) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
The compound represented by formula (2) is N, N-dibutyl-2-butenyl 1-amine, 1- (2-butenyl) from the viewpoint of reducing the hysteresis loss of the conjugated diene polymer composition of the present embodiment. Hexamethyleneimine is preferable, 1- (2-butenyl) piperidine and 1- (2-butenyl) hexamethyleneimine are more preferable, and 1- (2-butenyl) piperidine is more preferable.

The compound represented by the formula (3) is not limited to the following compounds. For example, N, N-dimethyl-o-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p- Toluidine, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dipropyl-o-toluidine, N, N-dipropyl-m- Toluidine, N, N-dipropyl-p-toluidine, N, N-dibutyl-o-toluidine, N, N-dibutyl-m-toluidine, N, N-dibutyl-p-toluidine, o-piperidinotoluene, p -Piperidinotoluene, o-pyrrolidinotoluene, p-pyrrolidinotoluene, N, N, N ', N'-tetramethyltoluylenediamine, N, N, N', N'-tetraethylto Irenamine, N, N, N ′, N′-tetrapropyltoluylenediamine, N, N-dimethylxylidine, N, N-diethylxylidine, N, N-dipropylxylidine, N, N-dimethylmesidine N, N-diethylmesidin, (N, N-dimethylamino) toluylphenylmethylamine, 1- (N, N-dimethylamino) -2-methylnaphthalene, 1- (N, N-dimethylamino) -2 -Methylanthracene.
The compound represented by the formula (3) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
The compound represented by the formula (3) is preferably N, N-dimethyl-o-toluidine from the viewpoint of reducing hysteresis loss of the modified conjugated diene polymer composition described later.

As the polymerization initiator system, the organolithium compound combined with the above-described compound having at least one nitrogen atom in the molecule is not limited to the following, but for example, n-butyllithium, sec-butyllithium, tert-butyl Lithium, n-propyllithium and iso-propyllithium are mentioned.
The organolithium compound constituting the polymerization initiator system has at least one nitrogen atom in the molecule and can be used as a polymerization initiator for anionic polymerization from the viewpoint of improving the modification rate and improving fuel efficiency. Yes, it preferably contains an organolithium compound represented by any one of the following general formulas (7) to (10).

In formula (7), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.

In formula (8), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure. R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms.

In formula (9), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected.
R ₁₅ and R ₁₆ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R ₁₆ represent an alkyl group having 5 to 12 carbon atoms and are branched to a part thereof. You may have a structure.

In formula (10), R ₁₇ forms a cyclic structure with a nitrogen atom, represents an alkyl group having 4 to 12 carbon atoms in total, and may have an unsaturated bond or a branched structure in a part thereof.
R ₁₈ represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.

In the formula (7), R ¹⁰ and R ¹¹ represent, but are not limited to, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, siltium group, ethylpropylamino Examples thereof include a lithium group, an ethylbutylaminolithium group, an ethylbenzylaminolithium group, and a methylphenethylaminolithium group.
R ¹⁰ and R ¹¹ are not limited to these, and include the similar compounds as long as the above conditions are satisfied. From the viewpoint of solubility in a solvent, reduction of hysteresis loss of the modified conjugated diene polymer composition of the present embodiment, and viewpoint of chain transfer reaction control described later, a dibutylaminolithium group and a dihexylaminolithium group are preferable, and more A dibutylamine group is preferred.
In the formula (7), when R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organolithium compound represented by the formula (7) is not limited to the following. Are, for example, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydro A pyridino lithium is mentioned. The organolithium compound represented by the formula (7) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoints of solubility of the polymerization initiator in the solvent, reduction of unpleasant odor of the modified conjugated diene polymer of the present embodiment, and suppression of chain transfer reaction, piperidinolithium, hexamethyleneiminolithium, lithium azacyclo Octane and lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, piperidinolithium or hexamethyleneiminolithium is more preferable, and piperidinolithium is more preferable. .

In the formula (8), R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms.
The conjugated diene polymer chain preferably represents a conjugated diene polymer chain having a repeating unit represented by any one of the following formulas (11) to (13).

In the formula (8), when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms, R ₁₄ has 2 to 16 carbon atoms from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. The alkylene group is preferably an alkylene group having 3 to 10 carbon atoms.

In addition, when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms, the organolithium compound represented by the formula (8) is not limited to the following, but for example, (3- (dimethylamino) -propyl ) Lithium, (3- (diethylamino) -propyl) lithium, (3- (dipropylamino) -propyl) lithium, (3- (dibutylamino) -propyl) lithium, (3- (dipentylamino) -propyl) lithium , (3- (dihexylamino) -propyl) lithium, (3- (dioctylamino) -propyl) lithium, (3- (ethylhexylamino) -propyl) lithium, (3- (didecylamino) -propyl) lithium, 3- (ethylpropylamino-propyl) lithium, (3- (ethylbutylamino-propyl) lithium, (3- Ethylbenzylamino) -propyl) lithium, (3- (methylphenethylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, (5- (dibutylamino) -pentyl) lithium, (6- ( And dibutylamino) -hexyl) lithium and (10- (dibutylamino) -decyl) lithium.
The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, (3- (dibutylamino) -propyl) lithium is more preferable.

In the formula (8), when R ₁₄ represents a conjugated diene polymer chain having a repeating unit represented by the formulas (11) to (13), the organolithium compound represented by the formula (8) is as follows: Although not limited to, for example, (4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (dibutylamino) -2-butenyl) Lithium, (4- (dipropylamino) -2-butenyl) lithium, (4- (diheptylamino) -2-butenyl) lithium, (4- (dihexylamino) -2-butenyl) lithium, (4- (Dioctylamino) -2-butenyl) lithium, (4- (di-2-ethylhexylamino) -2-butenyl) lithium, (4- (didecylamino) -2-butenyl) lithium, -(Ethylpropylamino) -2-butenyl) lithium, (4- (ethylbutylamino) -2-butenyl) lithium, (4- (ethylbenzylamino) -2-butenyl) lithium, (4- (methylphenethylamino) ) -2-butenyl) lithium, (4- (dimethylamino) -2-methyl-2-butenyl) lithium, (4- (diethylamino) -2-methyl-2-butenyl) lithium, (4- (dibutylamino) -2-methyl-2-butenyl) lithium, (4- (dipropylamino) -2-methyl-2-butenyl) lithium, (4- (diheptylamino) -2-methyl-2-butenyl) lithium, ( 4- (dihexylamino) -2-methyl-2-butenyl) lithium, (4- (dimethylamino) -3-methyl-2-butenyl) lithium, (4 (Diethylamino) -3-methyl-2-butenyl) lithium, (4- (dibutylamino) -3-methyl-2-butenyl) lithium, (4- (dipropylamino) -3-methyl-2-butenyl) lithium , (4- (diheptylamino) -3-methyl-2-butenyl) lithium and (4- (dihexylamino) -3-methyl-2-butenyl) lithium.
The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity as a polymerization initiator and the viewpoint of chain transfer reaction control described later, 4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (Dibutylamino) -2-butenyl) lithium is preferred, and (4- (dibutylamino) -2-butenyl) lithium is more preferred.

In the formula (8), when R ₁₂ and R ₁₃ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organic lithium compound represented by the formula (8) is limited to the following: For example, (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneiminyl) propyl) lithium, (3- (heptamethyleneiminyl) propyl) lithium, (3- (octamethylene) (Minyl) propyl) lithium, (3- (1,3,3-trimethyl-6-azabicyclo [3.2.1] octanyl) propyl) lithium, (3- (1,2,3,6-tetrahydropyridinyl) ) Propyl) lithium, (2- (hexamethineleniminyl) ethyl) lithium, (4- (hexamethineleniminyl) butyl) lithium, (5- (hexamethinelenine) (Minyl) pentyl) lithium, (6- (hexamethineleniminyl) hexyl) lithium, (10- (hexamethyleneleniminyl) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (Hexamethineleniminyl) -2-butenyl) lithium, (4- (heptamethyleneiminyl) -2-butenyl) lithium, (4- (octamethyleneiminyl) -2-butenyl) lithium, (4- ( 1,3,3-trimethyl-6-azabicyclo [3.2.1] octanyl) -2-butenyl) lithium, (4- (1,2,3,6-tetrahydropyridinyl) -2-butenyl) lithium , (4- (hexamethineleniminyl) -2-methyl-2-butenyl) lithium, (4- (hexamethineleniminyl) -3-methyl-2-butenyl) Lithium and the like.
The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, and from the viewpoint of chain transfer reaction control to be described later, (3- (piperidinyl) propyl) lithium, (3- (hexamethineleniminyl) propyl ) Lithium, (3- (1,2,3,6-tetrahydropyridinyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyneleniminyl) -2- Butenyl) lithium is preferred, more preferably (3- (hexamethyleneleniminyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyleneleniminyl) -2-butenyl) ) Lithium is preferred, and (4- (piperidinyl) -2-butenyl) lithium is more preferred.

The organolithium compound represented by the formula (9) is not limited to the following, but examples thereof include N, N-dimethyl-o-toluidinolithium, N, N-dimethyl-m-toluidinolithium, N, N-dimethyl-p-toluidinolithium, N, N-diethyl-o-toluidinolithium, N, N-diethyl-m-toluidinolithium, N, N-diethyl-p-toluidino Lithium, N, N-dipropyl-o-toluidinolithium, N, N-dipropyl-m-toluidinolithium, N, N-dipropyl-p-toluidinolithium, N, N-dibutyl-o-to Louisinolithium, N, N-dibutyl-m-toluidinolithium, N, N-dibutyl-p-toluidinolithium, o-piperidinotruenolithium, p-piperidinotruenolithium, o-pyrrole Notorenolithium, p-pyrrolidinotoluene, N, N, N ′, N′-tetramethyltoluylenediaminolithium, N, N, N ′, N′-tetraethyltoluylenediaminolithium, N, N, N ′, N'-tetrapropyltoluylenediaminolithium, N, N-dimethylxylidinolithium, N, N-diethylxylidinolithium, N, N-dipropylxylidinolithium, N, N-dimethylmesidinolithium, N, N -Diethylmesidinolithium, (N, N-dimethylamino) toluylphenylmethylaminolithium, 1- (N, N-dimethylamino) -2-methylnaphthalenolithium, 1- (N, N-dimethylamino) -2 -Methylanthracenolithium.
The organolithium compound represented by the formula (9) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of polymerization activity, N, N-dimethyl-o-toluidinolithium is more preferable.

The organolithium compound represented by the formula (10) is not limited to the following compounds. For example, 2- (2-methylpiperidinyl) -1-ethyllithium (for example, trade name “AI” manufactured by FMC Co., Ltd.) -250 ").
The organolithium compound represented by the formula (10) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  In the case where the conjugated diene polymer (a) is a modified product, before the polymerization step of the conjugated diene polymer in the state before the modification, as a polymerization initiator described above, at least one nitrogen atom is previously present in the molecule. An organolithium compound may be prepared, and the method is prepared by any known method.

  The organolithium compound having at least one nitrogen atom in the molecule represented by the formula (7), for example, reacts the compound represented by the formula (1) with the organolithium compound in a hydrocarbon solvent. Can be obtained. As the hydrocarbon solvent, an appropriate solvent such as hexane, cyclohexane, or benzene may be selected. The reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower, preferably 5.0 ° C. or higher and 70 ° C. or lower, more preferably 7.0 ° C. or higher and 50 ° C. or lower from the viewpoint of productivity.

The organolithium compound having at least one nitrogen atom in the molecule represented by the formula (8) is represented by, for example, the formula (2) when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms. By reacting a compound and an organolithium compound in a hydrocarbon solvent to prepare a lithium amide compound, this is reacted with an alkyl dihalide represented by the following formula (A), and further reacted with an organolithium compound. can get.

In formula (A), X ¹ and X ² each independently represent an I atom, a Br atom, or a Cl atom, and R ^3a represents an alkylene group having 1 to 20 carbon atoms, preferably 2 carbon atoms. Represents an alkylene group having ˜16, more preferably an alkylene group having 3 to 10 carbon atoms.

The compound represented by the formula (A) is not limited to the following compounds. For example, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo -6-chlorohexane, 1-bromo-10-chlorodecane, 1-bromo-3-iodopropane, 1-bromo-4-iodobutane, 1-bromo-5-iodopentane, 1-bromo-6-iodohexane, 1 -Bromo-10-iododecane, 1-chloro-3-iodopropane, 1-chloro-4-iodobutane, 1-chloro-5-iodopentane, 1-chloro-6-iodohexane, 1-chloro-10-iododecane Can be mentioned.
From the viewpoint of reactivity and safety, the compound represented by the formula (A) is 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6. -Chlorohexane and 1-bromo-10-chlorodecane are preferable, and 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane and 1-bromo-6-chlorohexane are more preferable.

  The reaction temperature when preparing the lithium amide compound using the compound represented by formula (2), the organic lithium compound, and the hydrocarbon solvent is preferably −78 ° C. or higher and 70 ° C. or lower. The reaction temperature when the compound represented by the formula (A) is reacted with the lithium amide compound is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower. Thereafter, the reaction temperature when the obtained compound is reacted with the organolithium compound is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower.

  The compound represented by Formula (9) can be manufactured using the compound represented by Formula (3), an organolithium compound, and a hydrocarbon solvent. The reaction temperature for preparing the lithium amide compound is preferably −78 ° C. or higher and 70 ° C. or lower. The reaction temperature when the compound represented by the formula (A) is reacted with the lithium amide compound is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower. Thereafter, the reaction temperature when the obtained compound is reacted with the organolithium compound is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower.

The organolithium compound represented by formula (8) having at least one nitrogen atom in the molecule is a conjugated diene in which R ₁₄ has a repeating unit represented by any one of formulas (11) to (13). When it represents a polymer chain, it is synthesized by the following steps (I) to (IV).
(I) A compound represented by the formula (2) and an organic lithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.
(II) The obtained lithium amide compound is reacted with butadiene or isoprene in a hydrocarbon solvent.
(III) Alcohol is added to deactivate lithium and the resulting product is distilled under reduced pressure.
(IV) The product obtained by distillation is reacted with an organolithium compound in a hydrocarbon solvent.
The reaction temperature of step (I) in which lithium amide is prepared using the compound represented by the formula (2), the organic lithium compound, and the hydrocarbon solvent is as described above.
As the alcohol in step (III), a general alcohol can be used, but a low molecular weight is preferable. For example, methanol, ethanol and isopropanol are preferable, and ethanol is more preferable.
The reaction temperature in step (IV) is 0 ° C. or higher and 80 ° C. or lower, preferably 10 ° C. or higher and 70 ° C. or lower.

When preparing the organolithium compound, a polar compound may be added to the system. There is a tendency to promote the formation and solubilization in a hydrocarbon solvent. Examples of the polar compound include, but are not limited to, the following: tertiary monoamines, tertiary diamines, chained or cyclic ethers.
The tertiary monoamine is not limited to the following, but examples include trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, N- Examples thereof include dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.
The tertiary diamine is not limited to the following, but examples thereof include N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropanediamine, N, N, N', N'-tetramethyldiaminobutane, N, N, N ', N'-tetramethyldiaminopentane, N, N, N', N'- Examples include tetramethylhexanediamine, dipiperidinopentane, and dipiperidinoethane.
Examples of the chain ether include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.
Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, 2 , 2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane.
Among polar compounds, tertiary monoamines such as trimethylamine and triethylamine; tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine, cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxolanyl) propane Is preferred. A polar compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When adding a polar compound when preparing an organolithium compound that is a polymerization initiator, it is preferably added within the range of 30 ppm to 50,000 ppm by mass with respect to the solvent used when preparing, It is more preferable to add in the range of mass ppm or more and 20,000 mass ppm or less. Addition of 30 mass ppm or more is preferable in order to fully express the effects of reaction promotion and solubilization in a solvent, ensuring the degree of freedom of microstructure adjustment in the polymerization step, and recovering the solvent after polymerization. Considering the separation from the polymerization solvent in the purification step, it is preferable to add at 50,000 mass ppm or less.

When the conjugated diene polymer (a) is a modified product, the conjugated diene polymer before the modification is the above-described various polymerization initiators, preferably an organic lithium compound having at least one nitrogen atom in the molecule, Alternatively, it is obtained by polymerizing with a conjugated diene compound using a polymerization initiator system containing a compound having at least one nitrogen atom and an organolithium compound, or by copolymerizing a conjugated diene compound and an aromatic vinyl compound. .
In the polymerization step, an organolithium compound having at least one nitrogen atom in the molecule is prepared in advance in a predetermined reactor, and polymerization of the conjugated diene compound or copolymerization of the conjugated diene compound and the aromatic vinyl compound is performed. The polymerization reaction may be carried out by supplying to a reactor that performs the above, or the above-mentioned compound having at least one nitrogen atom in the molecule and the organolithium compound are mixed and prepared using a static mixer or in-line mixer. A polymerization reaction may be performed. When using the organolithium compound which has at least 1 nitrogen atom in the molecule | numerator mentioned above as a polymerization initiator, the said compound may be used individually by 1 type, and may use 2 or more types of mixtures.
The conjugated diene polymer before modification is polymerized using a conjugated diene compound or a conjugated diene compound using a polymerization initiator system containing an organic lithium compound and a compound having at least one nitrogen atom in the molecule. And an aromatic vinyl compound.

The polymerization step of the conjugated diene polymer may be carried out by either a batch type or a continuous type polymerization method. However, a high modification rate, a high molecular weight, and a viewpoint of stably producing a highly branched conjugated diene polymer. Therefore, it is preferable to perform polymerization in a continuous mode, and it is more preferable to perform polymerization in a continuous mode in one reactor or two or more connected reactors.
At this time, in order to make the modification rate 75% by mass or more and MSR (stress relaxation) 0.45 or less, for example, the polymerization temperature is 45 ° C. or more and 80 ° C. or less and the solid content (solid content) is 16. It is preferable to make it 0 mass% or less.
In order to make the modification rate 78% by mass or more and the MSR 0.45 or less, the polymerization temperature should be controlled in the range of 50 ° C. or more and 80 ° C. or less, and the solid content should be 16.0% by mass or less. preferable.
In order to make the modification rate 80% by mass or more and MSR 0.44 or less, it is preferable to control the polymerization temperature in the range of 50 ° C. or more and 80 ° C. or less and to make the solid content 16.0% by mass or less. The feed composition of the organolithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent.
In order to achieve a modification rate of 85% by mass or more and an MSR of 0.43 or less, the polymerization temperature is controlled in the range of 50 ° C. or more and 78 ° C. or less, the solid content is 16.0% by mass or less, and organic The feed composition of the lithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent.
In order to make the modification rate 88% by mass or more and MSR 0.42 or less, the polymerization temperature is 55 ° C. or more and 76 ° C. or less, the solid content is 15.0% by mass or less, and the feed composition of the organolithium compound Is preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent.
More preferably, from the viewpoint of appropriately controlling the chain transfer reaction described below, achieving a modification rate of 90% by mass or more and an MSR of 0.40 or less, that is, achieving a high modification rate, high molecular weight, and high branching. Polymerization, the polymerization temperature is 60 ° C. or more and 72 ° C. or less, the solid content is 14.0% by mass or less, the organolithium compound is continuously added, and the feed composition of the organolithium compound is relative to the hydrocarbon solvent. Is preferably 0.00070 mol / L or less.

  The polymerization process of the polymer using the organolithium compound may be continuous or batch, but from the viewpoint of production efficiency, the monomer containing the conjugated diene compound and the polymerization initiator are continuously supplied to the polymerization tank. In addition, a continuous type that continuously polymerizes is preferable. In the case of a continuous type, the monomer, solvent, and polymerization initiator used for the polymerization may be fed separately to the polymerization tank, or a method using a mixing tank equipped with a stirrer, a static mixer or line in the pipe It may be a method of continuous mixing using a mixer.

  From the viewpoint of the stability of the organolithium compound, the monomer and polymerization initiator used for polymerization are preferably diluted with a hydrocarbon solvent. About a monomer, it is preferable that solid content is 16 mass% or less. When the polymerization initiator is an organic lithium compound, the feed composition of the organic lithium compound is preferably 0.0010 mol / L or less, more preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent.

  In the polymerization step, from the viewpoint of stable production of a high molecular weight polymer, it is preferable that the polymerization method is continuous and the organolithium compound is 0.0010 mol / L or less with respect to the hydrocarbon solvent.

  When performing polymerization in which a conjugated diene polymer becomes a copolymer of a conjugated diene compound and an aromatic vinyl compound using a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound In Makromol. As described in Chem 186. 1335-1350 (1985), the chain transfer reaction is promoted by the influence of at least one nitrogen atom in the molecule of the polymerization initiator system. Therefore, in order to increase the modification rate, specific production conditions tend to be required. Further, for example, when the polymerization temperature is increased, the chain transfer rate or the chain transfer rate is increased, the number average molecular weight of the obtained polymer is decreased, the degree of branching is increased, the molecular weight distribution is broadened, and the aromatic vinyl unit is increased. Since there is a tendency that the block portion linked by 30 or more tends to decrease or disappear, MSR tends to decrease. However, it is presumed that the inactivation of the living active terminal is promoted, and if the production conditions are not controlled, the modification rate tends to decrease. Note that, in each of the batch type polymerization method and the continuous type polymerization method, the continuous polymerization method tends to advance the chain transfer reaction.

  The polymerization temperature is not particularly limited as long as the anionic polymerization proceeds, the chain transfer reaction is controlled, and the number of blocks in which the aromatic vinyl compound units are linked is 30 or more, but it is not particularly limited. From the viewpoint of controlling the chain transfer reaction and ensuring a sufficient reaction amount of the modifier with respect to the active terminal after completion of the polymerization, it is more preferably 80 ° C. or less. From the viewpoint that the number of blocks in which 30 or more vinyl units are linked is small, 50 ° C. or higher and 78 ° C. or lower is more preferable, and 60 ° C. or higher and 75 ° C. or lower is even more preferable.

In the polymerization step, from the viewpoint of chain transfer reaction control, the solid is a content of the conjugated diene compound and the aromatic vinyl compound, and the total mass of the solvent, such as the conjugated diene compound and the aromatic vinyl compound. The content (also referred to as “monomer concentration”) is preferably 16% by mass or less, more preferably 15% by mass or less, and still more preferably 14% by mass or less. The upper limit of the solid content is not particularly limited, but is preferably 12.5% by mass or more.
In the polymerization step, from the viewpoint of chain transfer reaction control and suppression of active terminal deactivation, the polymerization method is continuous, the polymerization temperature is 45 ° C. or higher and 80 ° C. or lower, and the solid content is 16% by mass or less. Is preferred.

  The conjugated diene compound used in the polymerization step is not particularly limited. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl -1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more. In particular, 1,3-butadiene is preferable.

  The aromatic vinyl compound as a monomer used in the polymerization step is not limited to the following as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, p-methylstyrene, α-methyl Examples include styrene, vinyl ethylbenzene, vinyl xylene, vinyl naphthalene, and diphenyl ethylene. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  The polymerization step is preferably performed in a solvent. Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic carbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Hydrogen: Hydrocarbons composed of aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof.

The conjugated diene compound, the aromatic vinyl compound, and the polymerization solvent are each treated alone or mixed with these mixed solutions in advance before being subjected to a polymerization reaction by reacting the organometallic compound with allenes and acetylenes that are impurities. It is preferable to keep it.
Thereby, inhibition of polymerization by impurities can be prevented, the active terminal amount of the polymer becomes high, a sharper molecular weight distribution (Mw / Mn) can be achieved, and a higher modification rate tends to be achieved.

In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. Thereby, an aromatic vinyl compound can be copolymerized randomly with a conjugated diene compound, and it tends to be used as a vinylating agent for controlling the microstructure of the conjugated diene part. It is also effective in improving the polymerization rate.
Examples of polar compounds include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl). ) Ethers such as propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t-butylate, Examples include alkali metal alkoxide compounds such as sodium amylate; and phosphine compounds such as triphenylphosphine.
These polar compounds may be used alone or in combination of two or more.
The usage-amount of a polar compound is not specifically limited, Although it can select according to the objective etc., it is preferable that they are 0.01 mol or more and 100 mol or less with respect to 1 mol of polymerization initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of conjugated diene compounds and aromatic vinyl compounds, and tend to be used to adjust the distribution of aromatic vinyl compounds and adjust the amount of styrene block It is in.
As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently interrupted during the copolymerization. The method of adding automatically is mentioned.

When the conjugated diene polymer (a) is a modified product, the amount of bound conjugated diene in the conjugated diene polymer before the modification is not particularly limited, but as described above, 50% by mass or more and 100% by mass or less. It is preferable that it is 60 mass% or more and 80 mass% or less.
Further, the amount of bonded aromatic vinyl in the conjugated diene polymer is not particularly limited, but is preferably 0% by mass or more and 50% by mass or less, as described above, and is 20% by mass or more and 40% by mass or less. Is more preferable.
If the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate that has a better balance between low hysteresis loss and wet skid resistance, and that is more satisfactory in wear resistance and fracture strength can be obtained. It tends to be possible. Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it measures according to the method as described in the Example mentioned later.

  The vinyl bond amount in the conjugated diene bond unit of the conjugated diene polymer (a) is not particularly limited, but is preferably 10 mol% or more and 75 mol% or less, and 25 mol% or more and 65 mol% or less. Is more preferable. When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between low hysteresis loss and wet skid resistance and more satisfactory wear resistance and fracture strength tends to be obtained. Here, when the modified conjugated diene polymer is a copolymer of butadiene and styrene, in the butadiene bond unit by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond amount (1,2-bond amount) can be determined. Specifically, it is measured by the method described in the examples described later.

  The conjugated diene polymer before modification of the conjugated diene polymer (a) is not limited to the following, but for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer. Examples thereof include a polymer and a butadiene-isoprene-styrene random copolymer.

  The composition distribution of each monomer in the copolymer chain is not particularly limited. For example, a completely random copolymer close to a statistical random composition, a taper (gradient) random in which the composition is distributed in a tapered shape. A copolymer is mentioned. The bonding mode of the conjugated diene, that is, the composition of 1,4-bonds, 1,2-bonds, etc. may be uniform or distributed.

  If the conjugated diene compound contains allenes, acetylenes or the like as impurities, there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, and 50 ppm by mass or less based on the total amount of the conjugated diene compound. More preferably. Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

As described above, the microstructure (the amount of each bond in the conjugated diene copolymer (a)) is in the above range, and the glass transition temperature of the copolymer is in the range of −45 ° C. or more and −15 ° C. or less. In some cases, a better vulcanizate can be obtained due to the balance between low hysteresis loss and wet skid resistance.
Regarding the glass transition temperature, in accordance with ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature. Specifically, it is measured by the method described in the examples described later.

As described above, when the conjugated diene polymer (A) used in the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, the block of the block in which 30 or more aromatic vinyl units are linked. It is preferable that the number is small or absent.
Specifically, when the conjugated diene polymer (a) is a butadiene-styrene copolymer, the method described in Kolthoff's method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In the known method of decomposing a polymer by the method described in the above and analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are linked is preferably 5. It is 0 mass% or less, More preferably, it is 3.0 mass% or less.

(Modification process)
After obtaining a conjugated diene polymer having a polymerization active terminal by the method described above, a predetermined modifier is reacted with the polymerization active terminal, and a modification step is performed, thereby modifying the conjugated diene polymer. (In this specification, it may be described as a modified conjugated diene polymer (a)).
Preferably, a compound having a nitrogen atom in the molecule and having two or more epoxy groups (modifier), or a compound having an alkoxy group bonded to a silyl group in the molecule and having a nitrogen atom, which will be described later A modified conjugated diene polymer (A) is obtained by performing a modification step in which (modifier) is reacted.
In the modification step, the epoxy group of the compound having a nitrogen atom in the molecule and having an epoxy group (modifier) reacts with the polymerization active terminal of the conjugated diene polymer, so that the conjugated diene polymerization active terminal and A bond can be formed between the oxygen atoms of the ring-opened epoxy group.
In addition, the alkoxy group bonded to the silyl group of the compound (modifier) having an alkoxy group bonded to the silyl group in the molecule reacts with the polymerization active terminal of the conjugated diene polymer, A bond between the terminal of the conjugated diene polymer and Si can be formed. As a result, the modified conjugated diene polymer has a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent.

<Modifier>
Examples of the compound having a nitrogen atom in the molecule and having two or more epoxy groups (modifier) include compounds represented by the general formula (14).

In the general formula (14), R ¹⁹ and R ²⁰ are each a hydrocarbon group having 1 to 10 carbon atoms or an ether group and / or a hydrocarbon group having 1 to 10 carbon atoms having a tertiary amine, R ²¹ and R ²² are , Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms having an ether and / or a tertiary amine, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, or an ether, It is a C1-C20 hydrocarbon group which has at least 1 sort (s) of tertiary amine, epoxy, carbonyl, and halogen, and k is 1-6.
The modifier represented by the general formula (14) is preferably a compound having k of 2 or 3, for example, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane. Tetraglycidyl-1,3-bisaminomethylcyclohexane and the like.

  Moreover, as a compound (modifier) having an alkoxy group bonded to a silyl group in the molecule and having a nitrogen atom, for example, represented by general formula (15), general formula (16), or general formula (17) Compounds.

In the general formula (15), R ²⁴ and R ²⁵ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group, R ²⁶ is an alkylene group having 1 to 20 carbon atoms, and R ²⁷ , R ²⁸ is a hydrocarbon group having 1 to 6 carbon atoms which may be the same or different, and forms a ring structure of 5 or more members with two adjacent Ns, and R ²⁹ has a carbon number of 1 to 20 hydrocarbon groups or 3 organic substituted silyl groups, and p is an integer of 2 or 3.

In General Formula (16), R ^{31 to} R ³⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁵ represents an alkylene group having 1 to 10 carbon atoms. R ³⁶ represents an alkylene group having 1 to 20 carbon atoms. m is an integer of 1 or 2, and n is an integer of 2 or 3.

In the general formula (17), R ^{48 to} R ⁵⁰ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and R ^{51 to} R ⁵⁴ and R ⁵⁶ each independently represent 1 carbon atom. indicates 20 alkyl group, R ⁵⁵ and R ⁵⁸ each independently represents an alkylene group having 1 to 20 carbon atoms, R ⁵⁷ represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms, v represents an integer of 1 to 3, and w represents 1 or 2. R ^{48 to} R ⁵⁸ , v, and w when there are a plurality of each are independent and may be the same or different. d shows the integer of 0-6, e shows the integer of 0-6, f shows the integer of 0-6, (d + e + f) is the integer of 3-10. Y has at least one atom selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom, and has no active hydrogen. Represents an organic group. The hydrocarbon group represented by Y includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups. The organic group having no active hydrogen is an organic group that inactivates the active terminal of the conjugated diene polymer. Examples of such an organic group include functional groups having active hydrogen such as a hydroxyl group (—OH), a secondary amino group (> NH), a primary amino group (—NH ₂ ), and a sulfhydryl group (—SH). An organic group having no group.

  In the general formula (17), Y is represented by any one of the following general formulas (D) to (G).

In the general formula (D), Z ¹ is a single bond or a hydrocarbon group having a carbon number of 1 to 20, i represents the integer of 1 to 10. When there are a plurality of B ^{1 s} , they are independent of each other.

In the general formula (E), Z ² represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, Z ³ represents an alkyl group having 1 to 20 carbon atoms, and i represents an integer of 1 to 10 Show. Z ² and Z ³ in the case where there are a plurality of each are independent of each other.

In the general formula (F), Z ⁴ is a single bond or a hydrocarbon group having a carbon number of 1 to 20, i represents the integer of 1 to 10. When there are a plurality of Z ^{4 s} , they are independent of each other.

In general formula (G), Z < ⁵ > shows a single bond or a C1-C20 hydrocarbon group, and i shows the integer of 1-10. When there are a plurality of Z ^{5 s} , they are independent of each other.

  The modifier represented by the general formula (15) is not limited to the following, and examples thereof include 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- ( Diethoxyethylsilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) propyl] -3-ethylimidazo Lysine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxy) Silyl) propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) propyl] -1 Ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine, (2- {3- [3- (trimethoxysilyl) ) Propyl] tetrahydropyrimidin-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (dimethoxymethylsilyl) propyl] -4- (Trimethylsilyl) piperazine, 1- [3- (tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [ -(Dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxysilyl) Butyl] -4- (trimethylsilyl) piperazine and the like.

  Of these, 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (tri Methoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) Piperazine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine are preferred, and 1- [ 3- (Triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (triethoxysilyl) propyl] 4- (trimethylsilyl) piperazine are preferable.

  The modifier represented by the general formula (16) is not limited to the following, but for example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-sila Cyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza -2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl)- 1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2 Methyl-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclo Pentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) Examples include -1-aza-2-silacyclopentane.

  Among these, those in which m is 2 and n is 3 are more preferable from the viewpoints of rolling resistance characteristics and extrusion processability. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is preferred.

The modifying agent represented by the general formula (17) is not limited to the following, but examples include tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3- Tripropoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, Tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-methyl-1-sila-2-aza Kuropentan) propyl] -1,3-propanediamine,
Bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2) -Azacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tris (3-trimethoxysilylpropyl)-[3- (2, 2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-trimethoxysilylpropyl) -1,6-hexamethylenediamine, pentakis (3-trimethoxy Silylpropyl) -diethylenetriamine, tris (3-trimethoxysilylpropyl) -methyl 1,3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl) -bis [3- (2,2 -Dimethoxy-1-aza-2-silacyclopentane) propyl] silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) silane , Tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] silane 3-tris [2- (2,2-dimethoxy-1-aza-2-silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane, 1- 3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexane, 1- [3- (2, 2-dimethoxy-1-aza-2-silacyclopentane) propyl] -3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexane, 3,4,5-tris (3-trimethoxysilylpropyl) -Cyclohexyl- [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] ether, (3-trimethoxysilylpropyl) phosphate,
Bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate, bis [3- (2,2-dimethoxy-1-aza-2) -Silacyclopentane) propyl]-(3-trimethoxysilylpropyl) phosphate and tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate.

In Formula (17), the modifying agent in the case where Y is represented by Formula (D) is not limited to the following, but examples include tris (3-trimethoxysilylpropyl) amine, bis (3-tri Methoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) Propyl]-(3-trimethoxysilylpropyl) amine, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, tris (3-ethoxysilylpropyl) amine, bis ( 3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] amine, bis [3- (2,2-die Xyl-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) amine, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] amine, Tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]- 1,3-propanediamine, bis (3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine,
Tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-dimethoxy -1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-aza) Cyclopentane) propyl] -1,3-propanediamine, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- ( 1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis [3- (2,2-dimetho Ci-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1 , 3-propanediamine, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclo) Pentane) propyl] -1,3-propanediamine, tetrakis (3-triethoxysilylpropyl) -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1) -Aza-2-silacyclopentane) propyl] -1,3-propanediamine,
Bis (3-triethoxysilylpropyl) -bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2- Diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza-2-silacyclo) Pentane) propyl] -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3 -Propanediamine, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] [3- (1-Ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-sila Cyclopentane) propyl]-(3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3 -(2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3- Propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tris (3-trimethoxysilylpropylene )-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-trimethoxysilylpropyl) -bis [3- (2 , 2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -(3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, Tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) pro Pyr] -1,3-bisaminomethylcyclohexane, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1 -Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) Propyl]-(3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-silane) -2-Azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-triethoxysilylpropyl) -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- ( 2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-triethoxysilylpropyl) -bis [3- (2,2-diethoxy-1 -Aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxy Silylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza-2-silacy) Lopentane) propyl] -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3 -Bisaminomethylcyclohexane, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl) -1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3- Triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl ] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila) 2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-trimethoxysilylpropyl) -1,6-hexamethylenediamine, and pentakis (3-trimethoxysilylpropyl) -diethylenetriamine Can be mentioned.

The modifying agent in the case where Y is represented by the general formula (E) in the general formula (17) is not limited to the following, but for example, tris (3-trimethoxysilylpropyl) -methyl-1,3- Propanediamine, bis (2-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -methyl-1,3-propanediamine, bis [3- ( 2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -methyl-1,3-propanediamine, tris (3-triethoxysilylpropyl) -methyl-1 , 3-propanediamine, bis (2-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] Methyl-1,3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) -methyl-1,3-propanediamine ^{, N 1, N 1 '-} ( propane-1,3-diyl) bis (N ¹ - methyl -N ^3, N ³ - bis (3- (trimethoxysilyl) propyl) -1,3-propanediamine), and N ¹ - (3- (bis (3- (trimethoxysilyl) propyl) amino) propyl) -N ¹ - methyl -N ³ - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl ) -N ³ - (3- (trimethoxysilyl) propyl) -1,3-propane diamine.

  In the general formula (17), the modifying agent when Y is represented by the formula (F) is not limited to the following. For example, tetrakis [3- (2,2-dimethoxy-1-aza-2- Silacyclopentane) propyl] silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) silane, tris [3- (2,2 -Dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl) ) -Bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, (3-trimethoxysilyl)-[3- (1-methoxy-2) Trimethylsilyl-1-sila-2-azacyclopentane) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy-2-trimethylsilyl) -1-sila-2-azacyclopentane) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, tris (3-trimethoxysilylpropyl)-[3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-aza) Cyclopentane) propyl]-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy-) -Trimethylsilyl-1-sila-2-azacyclopentane) propyl] -bis (3-trimethoxysilylpropyl) silane and bis (3-trimethoxysilylpropyl) -bis [3- (1-methoxy-2-methyl) -1-sila-2-azacyclopentane) propyl] silane.

  In the general formula (17), the modifying agent in the case where Y is represented by the general formula (G) is not limited to the following. For example, 3-tris [2- (2,2-dimethoxy-1-aza -2-silacyclopentane) ethoxy] silyl-1- (2,2-dimethoxy-1-aza-2-silacyclopentane) propane, and 3-tris [2- (2,2-dimethoxy-1-aza-) 2-Silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane.

In the modifier of the general formula (17), Y is preferably represented by the general formula (D) or the general formula (E), and f is preferably 0. Such a modifier tends to be easily available, and tends to be more excellent in wear resistance and low hysteresis loss performance when the modified conjugated diene polymer is used as a vulcanizate.
Such modifiers are not limited to the following, but include, for example, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]. Amine, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2- Silacyclopentane) propyl] -1,3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-tri Methoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisamino Tylcyclohexane, tris (3-trimethoxysilylpropyl) -methyl-1,3-propanediamine, and bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3- Trismethoxysilylpropyl) -methyl-1,3-propanediamine.

In the modifier of the general formula (17), Y is represented by the general formula (D) or the general formula (E), f represents 0, and in the general formula (D) or the general formula (E), i is 2 What shows the integer of -10 is more preferable. Thereby, it exists in the tendency for the abrasion resistance and low hysteresis loss performance when vulcanized to become more excellent.
Such modifiers are not limited to the following, but include, for example, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, and N ^1- (3- (bis (3- (trimethoxy silyl) propyl) amino) propyl) -N ¹ - methyl -N ³ - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N ³ - (3- (trimethoxysilyl) propyl) -1,3-propanediamine.

  The reaction temperature, reaction time, and the like when the above-described modifier is reacted with the polymerization active terminal are not particularly limited, but are preferably reacted at 0 to 20 ° C. for 30 seconds or more.

  The amount of the compound represented by the general formula (17) can be adjusted so that the number of moles of the conjugated diene polymer and the number of moles of the modifier are reacted in a desired stoichiometric ratio. Therefore, the desired degree of branching tends to be achieved. The number of moles of the specific polymerization initiator is preferably 5.0 times mole or more, more preferably 6.0 times mole or more with respect to the mole number of the modifier. In this case, in the general formula (17), the number of functional groups ((v−1) × d + w × e + f) of the modifier is preferably an integer of 5 to 10, and more preferably an integer of 6 to 10. .

In the above-described modifiers other than the general formula (17), the total number of moles of epoxy groups in the compound or the total number of moles of alkoxy groups bonded to the silyl group is 0.8 to the number of moles of anionic polymerization initiator added. The range is preferably 3 times, more preferably 1 to 2.5 times, and even more preferably 1 to 2 times.
The resulting modified conjugated diene polymer (a) is preferably 0.8 times or more in order to obtain a sufficient modification rate, and a branched polymer obtained by coupling polymer ends to improve extrusion processability. In addition to obtaining the component, it is preferable to make it 3 times or less from the viewpoint of the modifier cost.

In the method for producing the modified conjugated diene polymer (A), a deactivation agent, a neutralizing agent and the like may be added to the polymer solution after the modification reaction, if necessary.
Examples of the quenching agent include water; alcohols such as methanol, ethanol, and isopropanol. Examples of the neutralizing agent include organic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.
The modified conjugated diene polymer (a) is preferably added with a rubber stabilizer from the viewpoint of preventing gel formation in the finishing step after polymerization and improving the stability during processing. The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4 ′ -Hydroxy-3 ', 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis [(octylthio) methyl] phenol and the like are preferable.

  Examples of the modified conjugated diene polymer (a) having a molecular structure branched from a nitrogen-containing epoxy substituent, produced as described above, include compounds represented by the following general formula (18).

In the general formula (18), (Polym) is a polymer chain, and R ^{19 to} R ²² and k have the same meaning as in the general formula (14).

  As the modified conjugated diene polymer (A) represented by the general formula (18), a compound in which k is 2 or 3 is particularly preferable. For example, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p- Examples include phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane, and the like.

  Examples of the modified conjugated diene polymer (a) having a molecular structure branched from a nitrogen-containing alkoxysilane substituent as produced above include, for example, the following general formula (19), general formula ( 20), compounds represented by the general formula (21), and the like.

In the general formula (19), (Polym) is a polymer chain, and R ^{25 to} R ²⁹ and p have the same meaning as in the general formula (15).

In general formula (20), (Polym) is a polymer chain, and R ^{30 to} R ³⁴ , m, and n are as defined in general formula (16).

In the general formula (21), (Polym) represents a diene polymer chain, R ^{61 to} R ⁶³ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, R ⁶⁴ and R ⁶⁷ Each independently represents an alkyl group having 1 to 20 carbon atoms, R ⁶⁵ , R ⁶⁸ and R ⁶⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁶⁶ and R ⁷⁰ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. v and K each independently represent an integer of 1 to 3, K ≦ v, w represents 1 or 2, L represents an integer of 1 to 3, and L ≦ (w + 1) , M represents an integer of 1 or 2. When there are a plurality of (Polym), R ^{61 to} R ⁷¹ , v, w, K, L, and M are each independent and may be the same or different. d represents an integer of 0-6, e represents an integer of 0-6, f represents an integer of 0-6, (d + e + f is an integer of 3-10, ((K × d ) + (L × e) + (M × k)) is an integer of 5 to 30. Y is a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a silicon atom, or a sulfur atom. And an organic group having at least one atom selected from the group consisting of phosphorus atoms and having no active hydrogen.

  Preferably, in the general formula (21), Y is represented by any one of the following general formulas (D) to (G).

In the general formula (D), Z ¹ is a single bond or a hydrocarbon group having a carbon number of 1 to 20, i represents the integer of 1 to 10. When there are a plurality of Z ^{1 s} , they are independent of each other.

In the general formula (E), Z ² represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, Z ³ represents an alkyl group having 1 to 20 carbon atoms, and i represents an integer of 1 to 10 Show. Z ² and Z ³ in the case where there are a plurality of each are independent of each other.

In the general formula (F), Z ⁴ is a single bond or a hydrocarbon group having a carbon number of 1 to 20, i represents the integer of 1 to 10. When there are a plurality of Z ^{4 s} , they are independent of each other.

In general formula (G), Z < ⁵ > shows a single bond or a C1-C20 hydrocarbon group, and i shows the integer of 1-10. When there are a plurality of Z ^{5 s} , they are independent of each other.

(Rubber components other than conjugated diene polymer (a))
The conjugated diene polymer composition of the present embodiment contains, in addition to the conjugated diene polymer (A) described above, other rubber-like polymers as rubber components within a range that satisfies the characteristics of the present embodiment. Also good.
Such a rubbery polymer is not limited to the following, but for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a Examples thereof include a hydrogenated product, a block copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, a non-diene polymer, and natural rubber.
Specific examples include natural rubber, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, and styrene-butadiene rubber or hydrogenated product thereof. Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin elastomers, butyl rubber, brominated butyl rubber, Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber and the like can be mentioned.
The various rubber-like polymers described above may be modified rubbers to which a functional group having a polarity such as a hydroxyl group or an amino group other than the modified conjugated diene polymer (A) is added. The weight average molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 1,500,000, from the viewpoint of the balance between performance and processing characteristics. Also, so-called liquid rubber having a low molecular weight can be used. These rubbery polymers may be used alone or in combination of two or more.
In the conjugated diene polymer composition of the present embodiment, the content ratio of the conjugated diene polymer (A) in the rubber component is preferably 5 to 100% by mass, more preferably 5 to 75% by mass, Preferably it is 20-70 mass%, More preferably, it is 30-70 mass%. When the content ratio of the modified conjugated diene polymer (a) in the rubber component is in the above range, a composition having an excellent balance between extrusion processability and rolling resistance characteristics can be obtained.

(Silica-based inorganic filler (b))
The conjugated diene polymer composition of the present embodiment contains a silica-based inorganic filler (B).
The silica-based inorganic filler (b) may be any “silica-based inorganic filler” that is generally used to promote steering stability due to the reinforcing effect of the conjugated diene polymer composition. Any “silica-based inorganic filler” used to exert the strength improvement effect of the rubber composition for treads can be widely adopted as an essential component of the conjugated diene polymer composition of the present embodiment.
The content of the silica-based inorganic filler (B) is not limited as long as the reinforcing effect of the conjugated diene-based polymer composition of the present embodiment can be obtained, but the conjugated diene-based polymer (A) 100 is not limited. 1-300 mass parts is preferable with respect to mass parts, 5-150 mass parts is more preferable, and 10-100 mass parts is further more preferable.

The silica-based inorganic filler used in the conjugated diene polymer composition of the present embodiment is not particularly limited, and known ones can be used, but a solid containing SiO ₂ or Si ₃ Al as a structural unit. Particles are preferred, and SiO ₂ or Si ₃ Al is more preferred as the main component of the structural unit.
Here, a main component means the component contained in a silica type inorganic filler 50 mass% or more, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more.
Specific examples of the silica-based inorganic filler (b) include inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable.
Examples of the dry silica include those obtained by reacting purified silicon tetrachloride in a high-temperature flame and having higher purity, finer particles, and extremely low moisture compared to the wet type. It is widely used as a raw material for fillers, resin thickeners, reinforcing agents, powder fluidizers and ceramics.
As wet silica, for example, sodium silicate using silica sand as a raw material, neutralizing the aqueous solution to deposit silica, filtering and drying, a fluffy and light white powder is given in appearance. In general, it is used as a reinforcing filler for synthetic rubber, prevention of powdering and consolidation of liquids such as agricultural chemicals, prevention of back-through of printing ink for lightweight paper, paint, ink thickening and anti-sagging, thermal insulation, and abrasive. .

In the conjugated diene polymer composition of this embodiment, from the viewpoint of obtaining more excellent rolling resistance characteristics, the nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler (b) is 100 to 300 m ² / It is preferable that it is g, and it is more preferable that it is 170-250 m < ² > / g.

  In the conjugated diene polymer composition of this embodiment, the viewpoint of developing rolling resistance characteristics by adding the silica-based inorganic filler (B), the viewpoint of developing steering stability, and the extrusion processability are practically sufficient. From the viewpoint of what is meant, the compounding amount of the silica-based inorganic filler (B) with respect to 100 parts by mass of the rubber component containing the conjugated diene polymer (A) is preferably 1 to 300 parts by mass, more preferably. It is 5-200 mass parts, More preferably, it is 20-150 mass parts.

(Hydrogenated copolymer (c))
The conjugated diene polymer composition of this embodiment contains a specific hydrogenated copolymer (c).
The specific hydrogenated copolymer (C) here is a hydrogenated non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit,
A polymer block (A) comprising vinyl aromatic monomer units;
It is obtained by hydrogenating a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit, that is, at least a hydrogenated product of the non-hydrogenated random copolymer block. One hydrogenated copolymer block (B),
And it is a hydrogenated copolymer which has a polymer block (A) at both ends.
The hydrogenated copolymer (c) has the following characteristics (1) and (2).
(1) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more.
(2) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c), the peak of loss tangent (tan δ) is attributed to the conjugated diene polymer (A) by differential scanning calorimetry (DSC). One exists only in the range from the crystallization peak temperature to below -10 ° C.

When the conjugated diene polymer composition of the present embodiment contains the hydrogenated copolymer (c), rolling resistance characteristics, wet grip properties, scorch resistance, and steering stability are improved.
The rolling resistance characteristics and wet grip properties are improved by including the hydrogenated copolymer (c), and compared with a conventionally used modified conjugated diene polymer composition containing a resin. It is considered that the dispersibility of the filler such as silica is improved by improving the compatibility with the component (a). When the hydrogenated copolymer (c) was blended with such a concept, the phenomenon that the scorch resistance and the steering stability of the conjugated diene polymer composition were improved was also found.

Hereinafter, the hydrogenated copolymer (c) will be described in detail.
The name of each monomer unit constituting the polymer is in accordance with the name of the monomer from which the monomer unit is derived. For example, “vinyl aromatic monomer unit” means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is substituted ethylene derived from a substituted vinyl group. It is a molecular structure in which the two carbons of the group are binding sites.
The term “conjugated diene monomer unit” means a structural unit of a polymer produced as a result of polymerizing a monomer, conjugated diene, and its structure is the same as that of an olefin derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.

The hydrogenated copolymer (c) is a non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit (hereinafter often referred to as “base non-hydrogenated copolymer”). It is hydrogenated.
The hydrogenated copolymer (c) comprises a polymer block (A) composed of vinyl aromatic monomer units, and a non-hydrogenated random copolymer composed of conjugated diene monomer units and vinyl aromatic monomer units. And at least one hydrogenated copolymer block (B) obtained by hydrogenating the combined block.

  From the viewpoint of impact absorption, the non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit preferably has a vinyl bond content of less than 40%, more preferably 50 % Or less, more preferably 30% or less, still more preferably 25% or less.

The polymer block (A) composed of vinyl aromatic monomer units plays a role like a physical cross-linking point and is therefore referred to as a “constrained phase”. In contrast, the hydrogenated copolymer block (B) is referred to as “unconstrained phase”.
The hydrogenated copolymer (c) has a polymer block (A) as a constrained phase at least at both ends. When the hydrogenated copolymer (c) has two or more polymer blocks (A) that are a constrained phase, the hydrogenated copolymer (c) has a large tensile stress and is excellent in handling stability.

The content of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is preferably 40% by mass to 60% by mass.
When the content of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is in the above range, flexibility and wet grip properties are excellent.
From the viewpoint of flexibility, the content of the vinyl aromatic monomer unit is more preferably more than 40% by mass and 80% by mass or less, still more preferably more than 45% by mass and 70% by mass or less, More preferably, it is more than 45 mass% and 60 mass% or less.

The content of vinyl aromatic monomer units in the hydrogenated copolymer (c) is almost equal to the content of vinyl aromatic monomer units in the base non-hydrogenated copolymer. The content rate of the body unit with respect to the hydrogenated copolymer (c) can be determined as the content rate with respect to the base non-hydrogenated copolymer.
The content of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) can be measured using an ultraviolet spectrophotometer using the base non-hydrogenated copolymer as a specimen.

Moreover, it is preferable that content of the polymer block (A) which consists of a vinyl aromatic monomer unit in a hydrogenated copolymer (c) is 0-60 mass%.
When the content of the polymer block (A) in the hydrogenated copolymer (c) is in the above range, the flexibility is excellent. From the viewpoint of flexibility and grip properties, the content of the polymer block (A) is more preferably 0 to 40% by mass, further preferably 1 to 40% by mass, and even more preferably 5 to 35% by mass, and more. More preferably, it is 10-30 mass%.
Furthermore, from the viewpoint of crosslinkability, the content of the polymer block (A) in the hydrogenated copolymer (c) is preferably less than 5% by mass, more preferably less than 2% by mass.

The content of the polymer block (A) in the hydrogenated copolymer (c) is substantially equal to the content of the polymer block (A) with respect to the base non-hydrogenated copolymer. The content rate with respect to the hydrogenated copolymer (c) can be determined as the content rate of the polymer block (A) with respect to the base non-hydrogenated copolymer.
Specifically, a method of oxidizing and decomposing a base non-hydrogenated copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 ( 1946), the mass of the vinyl aromatic polymer block component obtained by the method described below (often referred to as “osmium tetroxide decomposition method”) (however, the vinyl aromatic polymer component having an average degree of polymerization of about 30 or less is It is obtained from the following equation using
Content (% by mass) of vinyl aromatic polymer block (A) = (mass of vinyl aromatic polymer block (A) in base non-hydrogenated copolymer / mass of base non-hydrogenated copolymer) × 100.

  When the content of the polymer block (A) in the hydrogenated copolymer (C) is directly measured, a nuclear magnetic resonance apparatus (NMR) is used with the hydrogenated copolymer (C) as a specimen. (Method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as “NMR method”).

The content of the polymer block (A) determined by the osmium tetroxide decomposition method (referred to as “Os value”) and the content of the polymer block (A) determined by the NMR method (“Ns value”) Are referred to as correlations. As a result of investigations using various copolymers by the present inventors, it has been found that the relationship is expressed by the following formula.
Os value = −0.012 (Ns value) ² +1.8 Ns value) −13.0
Therefore, in the present invention, when the content (Ns value) in the hydrogenated copolymer (c) of the polymer block (A) is determined by NMR method, the Ns value is converted to the Os value based on the above formula. It can be converted.

  The content of the hydrogenated copolymer block (B) in the hydrogenated copolymer (c) is not particularly limited, but from the viewpoint of flexibility, the content of the hydrogenated copolymer block (B) is The hydrogenated copolymer (c) is preferably 30 to 95% by mass, more preferably 40 to 92% by mass, and still more preferably 50 to 90% by mass.

As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. is there.
Content of a hydrogenated copolymer block (B) is calculated | required from the addition amount of the conjugated diene monomer and vinyl aromatic monomer unit at the time of manufacturing the said non-hydrogenated random copolymer block.
The content of the hydrogenated copolymer block (B) with respect to the hydrogenated copolymer (c) is substantially equal to the content of the non-hydrogenated random copolymer block with respect to the base non-hydrogenated copolymer. The content of the hydrogenated copolymer block (B) with respect to the hydrogenated copolymer (c) can be determined as the content of the non-hydrogenated random copolymer block with respect to the base non-hydrogenated copolymer.

  The hydrogenated copolymer (c) preferably has a weight average molecular weight of 30,000 to 1,000,000. The hydrogenated copolymer (c) has an excellent balance between mechanical strength and moldability because the weight average molecular weight is in the above range. From the viewpoint of the balance between mechanical strength, handling stability and moldability, the weight average molecular weight of the hydrogenated copolymer (c) is preferably 50,000 to 800,000, more preferably 100,000 to 500,000, More preferably, it is 150,000 to 400,000.

  In the hydrogenated polymer (c), the molecular weight distribution (Mw / Mn) (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) is preferably 10 or less, more preferably 1 from the viewpoint of flexibility. 0.01 to 8, more preferably 1.1 to 5. When emphasizing molding processability, it is preferably 1.3 to 5, more preferably 1.5 to 5, still more preferably 1.6 to 4.5, and even more preferably 1.8 to 4.

Since the weight average molecular weight of the hydrogenated copolymer (c) is almost equal to the weight average molecular weight of the base non-hydrogenated copolymer, the weight average molecular weight of the hydrogenated copolymer (c) is the same as that of the base non-hydrogenated copolymer. It can obtain | require as a weight average molecular weight. The weight average molecular weight of the base non-hydrogenated copolymer can be determined by gel permeation chromatography (GPC) using a calibration curve obtained for a commercially available standard monodisperse polystyrene having a known molecular weight.
The number average molecular weight of the hydrogenated copolymer (c) can be determined in the same manner. The molecular weight distribution can be obtained by calculation as a ratio of the weight average molecular weight to the number average molecular weight.
As described above, the hydrogenated copolymer (c) is a non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic compound monomer unit (ie, a base non-hydrogenated copolymer). Is a hydrogenated base non-hydrogenated copolymer obtained by hydrogenation.
From the viewpoint of scorch resistance, the hydrogenation rate of the double bond of the conjugated diene monomer unit of the hydrogenated copolymer (c) is 75% or more, preferably 75 to 100%. From the viewpoint of scorch resistance and handleability (blocking resistance), the hydrogenation rate is more preferably 80 to 100%, still more preferably 85 to 100%, and even more preferably 90 to 100%.
Further, the hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated copolymer (c) is, as will be described later, using a known hydrogenation catalyst, a temperature range of 0 to 200 ° C., hydrogen The pressure can be controlled within the above numerical range by adjusting the pressure to 0.1 to 15 MPa and the hydrogenation reaction time to 3 to 10 hours.

  The hydrogenation rate of the vinyl aromatic monomer unit double bond in the hydrogenated copolymer (c) is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and still more preferably. 20% or less.

  The hydrogenation rate in the hydrogenated copolymer (c) can be measured using a nuclear magnetic resonance apparatus.

In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c), the hydrogenated copolymer (c) has a loss tangent (tan δ) peak determined by the differential scanning calorimetry (DSC). One exists only in the range from the crystallization peak temperature due to the system polymer (a) to less than -10 ° C.
The peak of the loss tangent existing in the range of the crystallization peak temperature due to the conjugated diene polymer (A) by differential scanning calorimetry (DSC) and lower than −10 ° C. is the hydrogenated copolymer block (B). This is a peak due to (hydrogenated polymer block obtained by hydrogenating a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit, a vinyl aromatic compound, and a monomer unit).
The loss tangent peak obtained for the hydrogenated copolymer (c) is not less than the crystallization peak temperature attributable to the conjugated diene polymer (a) by differential scanning calorimetry (DSC) and less than −10 ° C. The presence of only one in the range is necessary from the viewpoint of the balance between wet grip properties and rolling resistance properties of the hydrogenated copolymer (c).
The loss tangent (tan δ) peak in the dynamic viscoelastic spectrum is measured at a frequency of 10 Hz using a viscoelasticity analyzer.
Further, by controlling the number of hydrogenated copolymer blocks (B) and the mass ratio of the conjugated diene monomer unit and the vinyl aromatic monomer unit, the hydrogenated copolymer (c) can be obtained. In the dynamic viscoelastic spectrum, the loss tangent (tan δ) peak is 1 only in the range from the crystallization peak temperature due to the conjugated diene polymer (A) by differential scanning calorimetry (DSC) to less than −10 ° C. Can exist.

  As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit.

As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit.
The microstructure (the ratio of cis, trans, vinyl) of the conjugated diene monomer unit in the non-hydrogenated random copolymer can be arbitrarily controlled by using a polar compound described later.

The vinyl bond content of the conjugated diene monomer unit in the non-hydrogenated random copolymer block composed of the conjugated diene monomer unit and the vinyl aromatic monomer unit is less than 40% {hereinafter, 1, 2 -The total amount of vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds) is simply referred to as the amount of vinyl bonds. } Is preferred.
From the viewpoint of impact absorption, the non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit preferably has a vinyl bond content of less than 40%, more preferably 50 % Or less, more preferably 30% or less, still more preferably 25% or less.
The vinyl bond amount is measured using an infrared spectrophotometer using the base non-hydrogenated copolymer as a specimen.

As described above, the hydrogenated copolymer (c) has at least the polymer block (A) as a constrained phase at both ends and at least one hydrogenated copolymer block (B) as an unconstrained phase. Include.
When the hydrogenated copolymer (c) has the polymer block (A) as a constrained phase at both ends, the hydrogenated copolymer (c) has a small tensile residual strain. The tensile residual strain rate is preferably 50% or less, more preferably 30% or less, still more preferably 25% or less, and even more preferably 20% or less.
Here, the tensile residual strain ratio is a value (%) obtained by dividing the test piece in the tensile rupture test until it breaks, and dividing the residual elongation after rupture by 24 hours.

One embodiment of the hydrogenated copolymer (c) is a hydrogenated copolymer including at least the polymer block (A) at both ends and at least one hydrogenated copolymer block (B). However, examples of such a hydrogenated copolymer include those having a structure represented by the following formula.
A- (B-A) n
[(AB) n-A] m-X
In the above formula, each A independently represents a polymer block composed of vinyl aromatic monomer units.
Each B independently represents a hydrogenated copolymer block obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit.
The boundary of each block does not necessarily have to be clearly distinguished.
The vinyl aromatic monomer units in the hydrogenated copolymer block B obtained by hydrogenating the non-hydrogenated random copolymer block may be uniformly distributed or distributed in a tapered shape. Also good. The hydrogenated copolymer block (B) may have a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or portions where the vinyl aromatic monomer units are distributed in a tapered shape. In the hydrogenated copolymer block (B), a plurality of segments having different vinyl aromatic monomer unit contents may be present.
Each n is independently an integer of 1 or more, preferably an integer of 1 to 5.
Each m is independently an integer of 2 or more, preferably an integer of 2 to 11.
Each X independently represents a residue of a coupling agent or a residue of a polyfunctional initiator.
As the coupling agent, a bifunctional or higher functional coupling agent described later can be used.
As a polyfunctional initiator, a reaction product of diisopropenylbenzene and sec-butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene, or the like can be used.
The hydrogenated copolymer (c) may be any mixture having the structure represented by the above formula.

  As described above, the hydrogenated copolymer (c) has a loss tangent (tan δ) peak in the differential scanning calorimetry (DSC) in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c). 1) must be present only in the range from the crystallization peak temperature due to the conjugated diene polymer (a) to less than −10 ° C., and the loss tangent peak in the above range is hydrogenated. Copolymer block (B) (hydrogenated copolymer block obtained by hydrogenating a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit, a vinyl aromatic compound and a monomer unit) It is a peak due to it.

The conjugated diene constituting the hydrogenated copolymer (c) is a diolefin having a pair of conjugated double bonds.
Examples of the conjugated diene include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (that is, isoprene), 2,3-dimethyl-1,3-butadiene, 1 , 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are particularly preferred. These may be used alone or in combination of two or more.
Moreover, as a vinyl aromatic compound which comprises a hydrogenated copolymer (c), although not limited to the following, For example, styrene, (alpha) -methylstyrene, p-methylstyrene, divinylbenzene, 1,1 -Diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene. These may be used alone or in combination of two or more.

As described above, the hydrogenated copolymer (c) is obtained by hydrogenating a non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit.
There is no limitation in particular about the manufacturing method of the said non-hydrogenated copolymer, A well-known method can be used.
For example, it can be produced by anionic living polymerization using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent.
Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic such as cyclohexane, cycloheptane, and methylcycloheptane. Hydrocarbons; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

Examples of the polymerization initiator include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic aminoalkali metal compounds that have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds.
Examples of the alkali metal include lithium, sodium, and potassium.
Suitable organic alkali metal compounds are, for example, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and compounds containing at least one lithium in one molecule (monolithium compounds, dilithium compounds, trilithium compounds, Lithium compounds, tetralithium compounds, etc.). Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec A reaction product of -butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene can be used. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

  When an organic alkali metal compound is used as a polymerization initiator to copolymerize a conjugated diene monomer and a vinyl aromatic monomer, a vinyl bond (1,2 vinyl) resulting from the conjugated diene monomer unit incorporated in the polymer In order to adjust the amount of the bond or 3,4 vinyl bond) and the random copolymerization of the conjugated diene and the vinyl aromatic compound, a tertiary amine compound or an ether compound can be added as a regulator.

As the tertiary amine compound, for example, represented by the formula R 1 R 2 R 3 N (where R 1, R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms or a tertiary amino group). The compound which is made is mentioned.
Specifically, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine Etc.
Examples of ether compounds include linear ether compounds and cyclic ether compounds.
Examples of linear ether compounds include dimethyl ether, diethyl ether, diphenyl ether; ethylene glycol dialkyl ether compounds such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. And dialkyl ether compounds of diethylene glycol.
Examples of the cyclic ether compound include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and furfuryl alcohol. Of these alkyl ethers.

  The method of copolymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. Good. In particular, continuous polymerization is recommended for adjusting the molecular weight distribution to a preferable range in terms of moldability. The polymerization temperature is usually 0 to 180 ° C, preferably 30 to 150 ° C. The time required for the polymerization varies depending on other conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, it is necessary to pay attention so that impurities (water, oxygen, carbon dioxide, etc.) that inactivate the catalyst and the living polymer do not enter the polymerization system.

When the polymerization is completed, a coupling reaction can be performed using a bifunctional or higher functional coupling agent. There are no particular limitations on the bifunctional or higher functional coupling agent, and known coupling agents can be used.
Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates And acid esters.
Examples of the trifunctional or higher polyfunctional coupling agent include, but are not limited to, trihydric or higher polyalcohols; polyvalent epoxy compounds such as epoxidized soybean oil and diglycidyl bisphenol A; _4-n SiX _n (where each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a halogen atom, and n represents 3 or 4). A halogenated silicon compound such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof; the formula R _4-n SnX _n (where each R independently represents 1 carbon atom) -20 hydrocarbon groups, each X independently represents a halogen atom, n represents 3 or 4, and a tin halide compound such as methyltin trichloride, t-butyl And polyvalent halogen compounds such as rutin trichloride and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used as a polyfunctional coupling agent.

A hydrogenated copolymer (c) is obtained by hydrogenating the non-hydrogenated copolymer produced by the above method.
There is no limitation in particular in a hydrogenation catalyst, A well-known hydrogenation catalyst can be used. Examples of the hydrogenation catalyst include the following.
(1) A supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth,
(2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt together with a reducing agent such as organoaluminum, and (3) Ti, Ru, Rh, Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Zr.
Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841 (corresponding to US Pat. No. 4,501,857), Japanese Patent Publication No. Hydrogenation catalysts described in Japanese Patent No. 37970 (corresponding to US Pat. No. 4,673,714), Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041 can be used. Examples of preferred hydrogenation catalysts include titanocene compounds and mixtures of titanocene compounds and reducible organometallic compounds.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction for producing the hydrogenated copolymer (c) is usually carried out in a temperature range of 0 to 200 ° C, preferably 30 to 150 ° C.
The pressure of hydrogen used for the hydrogenation reaction is usually 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa.
The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.
The hydrogenation reaction can be used in any of batch processes, continuous processes, and combinations thereof.
A solution of the hydrogenated copolymer (c) is obtained by the hydrogenation reaction. The catalyst residue is removed from the hydrogenated copolymer (c) solution as necessary, and the hydrogenated copolymer (c) is separated from the solution. Examples of the method for separating the solvent include a method in which a polar solvent that is a poor solvent for the hydrogenated copolymer (c) such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer; Examples thereof include a method in which the reaction solution is poured into hot water with stirring and the solvent is removed by steam stripping; and a method in which the solvent is distilled off by directly heating the polymer solution.
In addition, stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers, and amine type stabilizers, can be added to the hydrogenated copolymer (c).

The hydrogenated copolymer (c) may be primary-modified.
Hereinafter, the primary-modified hydrogenated copolymer (c) will be described.
The primary-modified hydrogenated copolymer (C) includes a hydrogenated copolymer and a functional group-containing primary modifier group bonded to the hydrogenated copolymer.
The functional group-containing primary modifier group is bonded to at least one polymer chain end of the hydrogenated copolymer.
Examples of the functional group-containing primary modifier group include a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxylate group, an aldehyde group, a thioaldehyde group, and a carboxylate group. Amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, cyano group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, iso Examples thereof include those having at least one functional group selected from the group consisting of a thiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a halogenated tin group, an alkoxytin group, and a phenyltin group.
Of the above functional groups, a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group are preferable.

Examples of the modifier having the functional group are not limited to the following, but examples include tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, and tetraglycidyl. Diaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, N- (1,3-dibutylbutylidene) -3- (triethoxysilyl) -1-propanamine, 4-di (β-trimethoxysilylethyl) aminostyrene 4-di (β-triethoxysilylethyl) aminostyrene, 4-di (γ-trimethoxysilylpropyl) aminostyrene, 4-di (γ-triethoxysilylpropyl) aminostyrene, ε-caprolactone, δ- Valerolactone, butyrolactone, γ Cyclic lactones such as caprolactone, γ-valerolactone, 4-methoxybenzophenone, 4-ethoxybenzophenone, 4,4′-bis (methoxy) benzophenone, 4,4′-bis (ethoxy) benzophenone, γ-glycidoxyethyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyl Tributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxy Propylmethyl Ethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycid Xylpropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (Γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, Screw (γ Glycidoxypropyl) diphenoxy silane, bis (.gamma.-glycidoxypropyl) methyl mesylate silane, bis (.gamma.-glycidoxypropyl) methyl silane,
Further examples include bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycid Xylpropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) Dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3 , 4-epoxy Hexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) Propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl- Ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl -Methyldibutoxysilane, β- (3 4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,4-epoxy Silanes such as (cyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane,
1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone, 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- ( Diethoxyethylsilyl) propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methyl Hexahydropyrimidine, 3- [3- (tributoxysilyl) propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine Gin, 3- [3- (dimethoxymethylsilyl) propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl ] Imidazolidine, (2- {3- [3- (trimethoxysilyl) propyl] tetrahydropyrimidin-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) Piperazine, 1- [3- (dimethoxymethylsilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxy) Ethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl Pyr] -3- (trimethylsilyl) imidazolidine, 1- [3- (dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) ) Hexahydropyrimidine, 1- [4- (triethoxysilyl) butyl] -4- (trimethylsilyl) piperazine, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, Tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3- Triet Cysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- ( 5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy -1- (3-Diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclo Pentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-Dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, Tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-tripropoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl)-[3- (2,2- Dimethoxy-1-aza-2-silacyclopentane) propyl] amine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy) -2-Trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanedi Min, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-methyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis (3-triethoxy Silylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl ] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1- Aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-trimethoxysilylpro) ) -1,6-hexamethylenediamine, pentakis (3-trimethoxysilylpropyl) -diethylenetriamine, tris (3-trimethoxysilylpropyl) -methyl-1,3-propanediamine, tetrakis [3- (2,2 -Dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] Silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) silane, tris [3- (2,2-dimethoxy-1-aza -2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclo) Pentane) propyl] silane, 3-tris [2- (2,2-dimethoxy-1-aza-2-silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane, 1- [3- (1-methoxy-) 2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexane, 1- [3- (2,2-dimethoxy-1-aza) -2-silacyclopentane) propyl] -3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexane, 3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexyl- [3- ( 2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] ether, (3-trimethoxysilylpropyl) phosphate, bis 3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate, bis [3- (2,2-dimethoxy-1-aza-2-sila) Cyclopentane) propyl]-(3-trimethoxysilylpropyl) phosphate,
And tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate, tris (3-trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl)-[3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl] amine, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxy Silylpropyl) amine, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, tris (3-ethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl)- [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] amine, bis [3- (2,2-diethoxy- -Aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) amine, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] amine, tetrakis (3 -Trimethoxysilylpropyl) -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3 -Propanediamine, bis (3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris [3- ( 2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -1,3-propanedi , Tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy -2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2) -Silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis [3- (2,2-dimethoxy -1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1- Sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-) 2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-triethoxysilylpropyl) -1,3-propanediamine, tris (3-triethoxysilylpropyl) -[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, bis (3-triethoxysilylpropyl) -bis [3- (2,2- Diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-diethoxy-1-aza- -Silacyclopentane) propyl]-(3-triethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1, 3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis (3 -Triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclo Pentane) propyl] -1,3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) pro Ru]-(3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3- (2 , 2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, Tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl ] -1,3-bisaminomethylcyclohexane, bis (3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy) -1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3- Trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris (3- Trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-trimethoxysilylpropyl)- [3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2- Limethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3 -Trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2- Dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-triethoxysilylpropyl) -1,3-propanediamine, tris (3-triethoxysilylpropylene )-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-triethoxysilylpropyl) -bis [3- (2 , 2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -(3-triethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris ( 3-Triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3 -Bisaminomethylcyclohexane, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl) -1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3- Triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-diethoxy -1-Aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azashi) Lopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-trimethoxysilylpropyl) -1,6-hexamethylenediamine, and pentakis (3-trimethoxysilylpropyl) -diethylenetriamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxy Silylpropyl) silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) ) Propyl] silane, bis (3-trimethoxysilylpropyl) -bis [3- (2,2- Methoxy-1-aza-2-silacyclopentane) propyl] silane, (3-trimethoxysilyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) -bis [3 -(2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) -bis [3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl] silane, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) ) Propyl] silane, bis (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) pro Pyr]-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) Propyl] -bis (3-trimethoxysilylpropyl) silane and bis (3-trimethoxysilylpropyl) -bis [3- (1-methoxy-2-methyl-1-sila-2-azacyclopentane) propyl] Silane, 3-tris [2- (2,2-dimethoxy-1-aza-2-silacyclopentane) ethoxy] silyl-1- (2,2-dimethoxy-1-aza-2-silacyclopentane) propane, And 3-tris [2- (2,2-dimethoxy-1-aza-2-silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane and the like.

The primary-modified hydrogenated copolymer can be produced by modifying the hydrogenated copolymer, or can be produced by modifying the base non-hydrogenated copolymer and then hydrogenating it.
For example, when the base non-hydrogenated copolymer is modified and then hydrogenated, the primary modifier is added to the living terminal of the base non-hydrogenated copolymer obtained by the above method using an organolithium compound as a polymerization catalyst. A primary modified non-hydrogenated copolymer is obtained by reacting with the above, and a primary modified hydrogenated copolymer is obtained by hydrogenating the obtained primary modified non-hydrogenated copolymer.
In addition, a base non-hydrogenated copolymer having no living terminal is reacted with an organic alkali metal compound such as an organic lithium compound (metalation reaction) to obtain a copolymer having an organic alkali metal compound added to the terminal. And a method of subjecting the primary modifier to an addition reaction. In this case, after obtaining a hydrogenated product of the copolymer, a metallation reaction may be performed, and the primary modifier may be reacted to obtain a primary modified hydrogenated copolymer.

  Depending on the type of modifier, the hydroxyl group or amino group may be an organometallic salt at the stage of reaction of the primary modifier, but in such a case, it is a compound having active hydrogen such as water or alcohol. By treatment, a hydroxyl group, an amino group, or the like can be obtained.

  In any of the above modification methods, the reaction temperature is preferably 0 to 150 ° C, more preferably 20 to 120 ° C. The time required for the denaturation reaction varies depending on other conditions, but is preferably within 24 hours, particularly preferably 0.1 to 10 hours.

  After the primary modifier is reacted with the living terminal of the base non-hydrogenated copolymer, an unmodified copolymer may be mixed in the modified copolymer. The amount of the unmodified polymer mixed in the primary modified hydrogenated copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass with respect to the mass of the primary modified hydrogenated copolymer. It is below mass%.

Further, the hydrogenated copolymer (c) may be secondarily modified.
Here, the secondary-modified hydrogenated copolymer will be described.
The secondary modified hydrogenated copolymer is obtained by reacting a secondary modifier with the primary modified hydrogenated copolymer, and the secondary modifier is a primary modified hydrogenated copolymer. The polymer has a functional group reactive with the functional group of the primary modifier group.
Preferable examples of the functional group of the secondary modifier include at least one selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group.
The secondary modifier preferably has at least two types of the above functional groups. However, when the functional group is an acid anhydride group, a secondary modifier having only one acid anhydride group is particularly preferable. When the secondary modifier is reacted with the primary modified hydrogenated copolymer, the amount of the secondary modifier is usually 0. 0 per equivalent of the functional group of the primary modifier bonded to the primary modified hydrogenated copolymer. 3 to 10 mol, preferably 0.4 to 5 mol, more preferably 0.5 to 4 mol.

The method of reacting the secondary modifier with the primary modified hydrogenated copolymer is not particularly limited, and a known method can be used.
Examples thereof include a melt-kneading method described later and a method of reacting each component by dissolving or dispersing in a solvent or the like.
In the method of reacting each component dissolved or dispersed in a solvent or the like, the solvent is not particularly limited as long as it dissolves or disperses each component. For example, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic In addition to hydrocarbon solvents such as group hydrocarbons, halogen-containing solvents, ester solvents, ether solvents and the like can be used. In such a method, the temperature at which the secondary modifier is reacted with the hydrogenated copolymer that has been primarily modified is usually −10 to 150 ° C., preferably 30 to 120 ° C. The time required for the reaction varies depending on other conditions, but is usually within 3 hours, preferably several seconds to 1 hour. A particularly preferable method is a method of obtaining a secondary modified hydrogenated copolymer by adding a secondary modifier to the solution of the produced primary modified hydrogenated copolymer. In this case, the solution of the primary-modified hydrogenated copolymer may be neutralized and then reacted with the secondary modifier.

Examples of the secondary denaturant include the following.
Examples of secondary modifiers having a carboxyl group include aliphatic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid. Carboxylic acids; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.
Examples of the secondary modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5. -Benzenetetracarboxylic dianhydride, 5- (2,5-dioxytetrahydroxyfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic-dicarboxylic anhydride.

Examples of the secondary modifier having an isocyanate group include toluylene diisocyanate, diphenylmethane diisocyanate, and polyfunctional aromatic isocyanate.
Examples of the secondary modifier having an epoxy group include tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, and terephthalic acid. A diglycidyl ester acrylate is mentioned.
Furthermore, said epoxy compound described as a primary modifier used in order to obtain a primary modified hydrogenated copolymer is mentioned.
Examples of the secondary modifier having a silanol group include hydrolysates of the above alkoxysilane compounds described as primary modifiers used to obtain a primary modified hydrogenated copolymer.

Examples of the secondary modifier having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, and ethoxysiloxane oligomers. Furthermore, said silane compound described as a primary modifier used in order to obtain a primary modified hydrogenated copolymer is mentioned.
Particularly preferred secondary modifiers include, for example, carboxylic acids having two or more carboxyl groups or acid anhydrides thereof, and two or more acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilane groups. A crosslinking agent is mentioned. Specific examples include maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, bis- ( 3-triethoxysilylpropyl) -tetrasulfane.

Hydrogenated copolymer (unmodified hydrogenated copolymer) (c) may be graft-modified with α, β-unsaturated carboxylic acid or a derivative thereof such as an anhydride, esterified product, amidated product or imidized product thereof. Can do. Examples of the α, β-unsaturated carboxylic acid or derivative thereof include maleic anhydride, maleic imide, acrylic acid or ester thereof, methacrylic acid or ester thereof, endo-cis-bicyclo [2,2,1]- 5-heptene-2,3-dicarboxylic acid or its anhydride is mentioned.
The addition amount of the α, β-unsaturated carboxylic acid or derivative thereof is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass per 100 parts by mass of the hydrogenated copolymer.
The reaction temperature for graft modification is preferably 100 to 300 ° C, more preferably 120 to 280 ° C.
For details of the graft modification method, reference can be made to, for example, JP-A No. 62-79211.

By reacting the primary modified hydrogenated copolymer or the secondary modified hydrogenated copolymer with a functional oligomer having reactivity with the functional group of the primary modifier or the secondary modifier, an oligomer modified hydrogenated product is obtained. A copolymer can be obtained.
The functional group of the functional oligomer is not particularly limited as long as it is a functional group reactive with the functional group bonded to the primary modified hydrogenated copolymer or the secondary modified hydrogenated copolymer. .
Preferred examples of the functional oligomer include a functional oligomer having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Is mentioned. The number average molecular weight of these functional oligomers is usually 300 or more and less than 3,0000, preferably 500 or more and less than 15,000, more preferably 1,000 or more and less than 20,000.
There are no particular limitations on the method for producing these functional oligomers, and any known method can be used. For example, it can be produced by an anionic polymerization method, a cationic polymerization method, a radical polymerization method, a condensation polymerization method, a polyaddition reaction, or the like.
Examples of the functional oligomer include a butadiene oligomer having at least one functional group or a hydrogenated product thereof, an isoprene oligomer having at least one functional group or a hydrogenated product thereof, and an ethylene oligomer having at least one functional group. , Propylene oligomer having at least one functional group, ethylene oxide oligomer, propylene oxide oligomer, ethylene oxide-propylene oxide copolymer oligomer, saponified ethylene-vinyl acetate copolymer oligomer, functionality having at least one functional group Examples thereof include copolymer oligomers of vinyl monomers and other vinyl monomers that can be copolymerized therewith.

(Carbon black)
The conjugated diene polymer composition of the present embodiment preferably further contains carbon black, and more preferably contains 0.5 to 100 parts by mass of carbon black with respect to 100 parts by mass of the rubber component.
The carbon black is not particularly limited, and for example, carbon blacks of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, a carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or more is preferable from the viewpoint of extrusion moldability and rolling resistance characteristics.
The compounding amount of the carbon black is 100 parts by mass of the rubber component containing the conjugated diene polymer (A) from the viewpoint of developing rolling resistance characteristics by adding the silica-based inorganic filler (B) and from the viewpoint of extrusion processability. On the other hand, 0.5-100 mass parts is preferable, 3-100 mass parts is more preferable, and 5-50 mass parts is further more preferable.

(Metal oxide and metal hydroxide)
The conjugated diene polymer composition of the present embodiment may contain a metal oxide or a metal hydroxide in addition to the silica-based inorganic filler (b) and carbon black.
The metal oxide refers to solid particles whose main component is a chemical unit M _x O _y (M represents a metal atom, and x and y each represent an integer of 1 to 6). Alumina, titanium oxide, magnesium oxide, zinc oxide, or the like can be used.
A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used.
The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

(Silane coupling agent)
Since the conjugated diene polymer composition of this embodiment contains a silica-based inorganic filler (B), it is preferable to add a silane coupling agent.
Although the silane coupling agent is not limited to the following, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik Degussa: Si363], Momentive NXT-Z30, NXT-Z45, Silane coupling agents containing mercapto groups such as NXTZ60, NXT silane, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis -[2- (triethoxysilyl -Ethyl] -tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis ( 2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N , N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxy Methylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like.
In particular, bis- [3- (triethoxysilyl) -propyl] -disulfide, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik Degussa: Si363], Momentive's NXT-Z30, NXT-Z45, NXTZ60, silane coupling agents containing mercapto groups such as NXTsilane, bis- [3- (triethoxysilyl) -propyl] -tetra Sulfide is preferred because of its high reinforcing effect.
These silane coupling agents can be used singly or in combination of two or more.
The blending amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the silica-based inorganic filler (b) described above, and 1 to 15 Part by mass is more preferable. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent can be made more remarkable.

(Rubber softener)
In order to improve processability, the conjugated diene polymer composition of the present embodiment may contain a rubber softener.
As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable.
A mineral oil-based rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic rings, naphthene rings, and paraffin chains. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system. As the rubber softener used together with the modified conjugated diene-aromatic vinyl copolymer, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.
The blending amount of the rubber softener is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and more preferably 30 to 90 parts by weight with respect to 100 parts by weight of the rubber component containing the conjugated diene polymer (A). Part is more preferred.
When the blending amount of the rubber softener is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, the occurrence of bleed out can be prevented and the surface of the conjugated diene polymer composition of this embodiment is sticky. Can be prevented.

(Kneading method and other additives)
In producing the conjugated diene polymer composition of this embodiment, the conjugated diene polymer (A) and other rubbery polymers, silica-based inorganic fillers (B), and the hydrogenated copolymer (C) The method of mixing additives such as carbon black and other fillers, silane coupling agents, rubber softeners and the like is not particularly limited.
For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc. The method of removing by heating, etc. are mentioned.
Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties.
In addition, any of a method of kneading the conjugated diene polymer (A) and various compounding agents at a time and a method of mixing in a plurality of times can be applied.

The conjugated diene polymer composition of the present embodiment may be a vulcanized rubber composition obtained by vulcanizing a non-vulcanized rubber composition with a vulcanizing agent.
As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used.
Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like.
The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the conjugated diene polymer (A). A conventionally known method can be applied as the vulcanization method, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.
In vulcanization, a vulcanization accelerator may be used as necessary. As the vulcanization accelerator, conventionally known materials can be used. For example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like. Further, as the vulcanization aid, zinc white, stearic acid or the like can be used. The usage-amount of a vulcanization accelerator is 0.01-20 mass parts normally with respect to 100 mass parts of rubber components containing a conjugated diene polymer (I), and 0.1-15 mass parts is preferable.

In the conjugated diene polymer composition of the present embodiment, other softeners and fillers other than those described above, as well as heat stabilizers, antistatic agents, and weather resistance stability, within the range not impairing the purpose of the present embodiment. Various additives such as an agent, an anti-aging agent, a coloring agent, and a lubricant may be used.
As other softeners, known softeners can be used.
Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
Known materials can be used as the above heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant.

The conjugated diene polymer composition of the present embodiment is suitable for a base tread, and is suitable for a tire application including a base tread containing a crosslinked product of the conjugated diene polymer of the present embodiment.
That is, a tire can be manufactured by manufacturing a base tread using the conjugated diene polymer composition of this embodiment, bonding together with other members, and heating and pressing using a tire molding machine. .
By using the modified conjugated diene polymer as the conjugated diene polymer, it is possible to produce a tire with a high balance of rolling resistance characteristics and wet grip properties. In addition to the base tread, the composition containing the modified conjugated diene polymer can be used for other parts of the tire such as sidewalls, carcass, and shoulders.

Hereinafter, the present embodiment will be described in more detail with specific examples and comparative examples. However, the present embodiment is not limited to the following examples.
In Examples and Comparative Examples, a non-hydrogenated copolymer is hydrogenated to obtain a hydrogenated copolymer.
As described above, this non-hydrogenated copolymer may be referred to as “base non-hydrogenated copolymer” in the present specification.
In Examples and Comparative Examples, the structure and physical properties of the polymers were measured by the methods shown below.

(Physical property 1) Modification rate of conjugated diene polymer (a) (Modification rate due to adsorption to silica gel)
Using the conjugated diene polymer (A) as a sample, the measurement was performed by applying the property of adsorbing the modified basic polymer component to a GPC column using silica gel as a filler.
The amount of adsorption on the silica column is measured from the difference between the chromatogram measured with the polystyrene column and the chromatogram measured with the silica column of the sample solution containing the sample and the low molecular weight internal standard polystyrene. Asked.
Specifically, it is as shown below.
It measured on the following measurement conditions.
-Preparation of sample solution: 10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of THF to prepare a sample solution.
Measurement conditions: Measurement was performed by injecting 20 μL of the sample solution into the apparatus using THF containing 5 mmol / L of triethylamine as an eluent. As the column, guard column: trade name “TSKguardcolumn SuperH-H” manufactured by Tosoh Corporation, column: trade name “TSKgel SuperH5000”, “TSKgel SuperH6000”, “TSKgel SuperH7000” manufactured by Tosoh Corporation were used. A chromatogram was obtained by measurement using a RI detector (HLC8020 manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 0.6 mL / min.
GPC measurement conditions using a silica column: Using a trade name “HLC-8320GPC” manufactured by Tosoh Corporation, THF is used as an eluent, 50 μL of a sample solution is injected into the apparatus, a column oven temperature of 40 ° C., a THF flow rate A chromatogram was obtained using an RI detector at 0.5 ml / min. The column uses the product names “Zorbax PSM-1000S”, “PSM-300S”, “PSM-60S” and uses the product name “DIOL 4.6 × 12.5 mm 5 micron” as a guard column in the front stage. Connected and used.
Calculation method of denaturation rate: The total peak area of the chromatogram using the polystyrene column is 100, the peak area of the sample is P1, the peak area of the standard polystyrene is P2, and the peak area of the chromatogram using the silica column is With the total as 100, the peak area of the sample was P3, and the peak area of standard polystyrene was P4, and the modification rate (%) was determined from the following formula.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)

(Physical property 2) Styrene content in hydrogenated copolymer (c) The content of styrene monomer units relative to the hydrogenated copolymer (c) is determined by ultraviolet spectrophotometry using the base non-hydrogenated copolymer as a specimen. It measured using the meter (UV-2450; Shimadzu Corporation make).
The content of the styrene monomer unit with respect to the hydrogenated copolymer was determined as the content of the styrene monomer unit with respect to the base non-hydrogenated copolymer.
In addition, when using a hydrogenated copolymer as a test substance, it measured using the nuclear magnetic resonance apparatus (Germany BRUKER company make, DPX-400).
The measurement results are shown in Table 1.

(Physical property 3) Content of styrene polymer block (A) in hydrogenated copolymer (c) (Os value)
The styrene polymer block content of the non-hydrogenated copolymer is M. Kolthoff, et al. , J .; Polym. Sci. 1, 429 (1946).
For the decomposition of the non-hydrogenated copolymer, a 0.1 g / 125 ml tertiary butanol solution of osmic acid was used. The styrene polymer block content obtained here is referred to as “Os value”.
In the case of measuring the styrene polymer block content of the hydrogenated copolymer, a nuclear magnetic resonance apparatus (JMN-270WB; manufactured by JEOL Ltd.) was used. Measured according to the method described in Tanaka, et al., RUBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Specifically, 1H-NMR was measured using a sample obtained by dissolving 30 mg of a hydrogenated copolymer in 1 g of deuterated chloroform.
The styrene polymer block content (Ns value) of the hydrogenated copolymer obtained by NMR measurement is the total integrated value, the integrated value of chemical shift 6.9 to 6.3 ppm, and the chemical shift 7.5 to 6.9 ppm. The Ns value was converted into an Os value.
The calculation method is shown below.
Block styrene (St) strength = (6.9 to 6.3 ppm) integrated value / 2
Random styrene (St) strength = (7.5-6.9 ppm) integrated value -3 (block St strength)
Ethylene / Butylene (EB) Strength = Total Integrated Value-3 {(Block St Strength) + (Random St Strength)} / 8
Styrene polymer block content obtained by NMR measurement (Ns value)
= 104 (Block St intensity) / [104 {(Block St intensity) + (Random St intensity)} + 56 (EB intensity)]
Os value = −0.012 (Ns value) ² +1.8 (Ns value) −13.0

(Physical property 4) Content of hydrogenated copolymer block (B) obtained by hydrogenating non-hydrogenated random copolymer block in hydrogenated copolymer (c) Hydrogenated copolymer (c) The content of the hydrogenated copolymer block (B) therein was determined from the addition amounts of the conjugated diene monomer and the vinyl aromatic monomer unit when producing the non-hydrogenated random copolymer block.
The content of the hydrogenated copolymer block (B) with respect to the hydrogenated copolymer (c) was determined as the content of the non-hydrogenated random copolymer block with respect to the base non-hydrogenated copolymer.

(Physical property 5) Vinyl bond amount of non-hydrogenated random copolymer block and vinyl bond amount of conjugated diene portion of hydrogenated copolymer (B) contained in hydrogenated copolymer (c) Base non-hydrogenated copolymer The amount of vinyl bonds in the polymer block in the polymer was measured using an infrared spectrophotometer (FT / IR-230; manufactured by JASCO Corporation).
The vinyl bond amount of the conjugated diene polymer block which is a homopolymer block was calculated by the Morero method.
The vinyl bond amount of the conjugated diene / styrene copolymer block, which is a copolymer block, was calculated by the Hampton method.
In addition, when measuring the amount of vinyl bonds using a hydrogenated copolymer, it measured using the nuclear magnetic resonance apparatus (DPX-400; German BRUKER company make).

(Physical property 6) Weight average molecular weight and molecular weight distribution of hydrogenated copolymer (c) The weight average molecular weight of hydrogenated copolymer (c) is almost equal to the weight average molecular weight of the base non-hydrogenated copolymer. The weight average molecular weight of the additive copolymer (c) was determined as the weight average molecular weight of the base non-hydrogenated copolymer.
The weight average molecular weight of the base non-hydrogenated copolymer was measured by GPC (using an apparatus manufactured by Waters, USA).
Tetrahydrofuran was used as a solvent, and the temperature was measured at 35 ° C.
The weight average molecular weight was calculated | required from the GPC chromatogram using the calibration curve created using the commercially available standard monodisperse polystyrene type gel with known molecular weight.
The number average molecular weight was determined from the GPC chromatogram.
The molecular weight distribution was determined as the ratio of the obtained weight average molecular weight (Mw) to the obtained number average molecular weight (Mn).

(Physical property 7) Denaturation rate of hydrogenated copolymer (c) The modified copolymer has the property of adsorbing to a silica gel column but not adsorbing to a polystyrene gel column. Utilizing this characteristic, the denaturation rate was measured as follows.
Regarding the sample solution containing the sample (modified copolymer) and the low molecular weight internal standard polystyrene, GPC of the same standard polystyrene gel column (Shodex; manufactured by Showa Denko) column as described in the above physical property 1) and silica type Both chromatograms were measured by performing GPC on a gel column (Zorbax; manufactured by DuPont, USA).
The amount of adsorption on the silica column was measured from the difference, and the modification rate was determined.

(Physical property 8) Hydrogenation rate of double bond of conjugated diene monomer unit of hydrogenated copolymer (c) The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (DPX-400; manufactured by BRUKER, Germany). It was measured.
The measurement results are shown in Table 1.

(Physical property 9) Peak temperature of tan δ of hydrogenated copolymer (c) It was determined by measuring the viscoelastic spectrum using a viscoelasticity measuring and analyzing apparatus (model DVE-V4; manufactured by Rheology Co., Ltd.). The measurement frequency is 10 Hz.
The measurement results are shown in Table 1.

(Physical property 10) Scorch resistance The sample used was the unvulcanized rubber composition produced in the examples and comparative examples described below, which was left in a room at 23 ° C for 12 hours.
A Mooney scorch test (130 ° C.) was performed using a Mooney viscometer SMV-201 manufactured by Shimadzu Corporation according to JIS-K6300-1, and a scorch time (t5, min) was measured.
Each measured value is set to 100 for Comparative Example 1 for Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 9 and 10, and Comparative Example 4 for Example 7 and Comparative Examples 4 to 7. As for 100, Example 8 and Comparative Example 8 were quantified with Comparative Example 8 as 100.
Higher values indicate better scorch resistance (early vulcanization is less likely to occur and processability is better).

(Physical property 11) Rolling resistance characteristic The viscoelasticity parameter was measured by the torsion mode using the viscoelasticity testing machine (ARES-G2) by TA Instruments.
Each measured value is set to 100 for Comparative Example 1 for Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 9 and 10, and Comparative Example 4 for Example 7 and Comparative Examples 4 to 7. As for 100, Example 8 and Comparative Example 8 were quantified with Comparative Example 8 as 100.
Tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of rolling resistance characteristics (low fuel consumption). A smaller value indicates better rolling resistance characteristics.

(Physical property 12) Wet grip property Viscoelasticity parameters were measured in a torsion mode using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments.
Each measured value is set to 100 for Comparative Example 1 for Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 9 and 10, and Comparative Example 4 for Example 7 and Comparative Examples 4 to 7. As for 100, Example 8 and Comparative Example 8 were quantified with Comparative Example 8 as 100.
Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip properties. It shows that wet grip property is so favorable that a value is large.

(Physical property 13) Steering stability Using the obtained vulcanized rubber test piece, a dumbbell JIS No. 5 test piece was prepared according to JIS-K6251 and pulled at a tensile speed of 500 mm / min at room temperature (23 ° C.). The test was performed and the 100% tensile stress at 100% elongation was measured.
Each measured value is set to 100 for Comparative Example 1 for Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 9 and 10, and Comparative Example 4 for Example 7 and Comparative Examples 4 to 7. As for 100, Example 8 and Comparative Example 8 were quantified with Comparative Example 8 as 100.
The larger this index, the better the steering stability.

  In Production Examples 1 to 4 and 6, the hydrogenation catalyst used for the hydrogenation reaction of the hydrogenated copolymer (c) was produced as follows.

[Production of hydrogenation catalyst]
A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and 1,2-polybutadiene having a molecular weight of about 1,000. 150 g of (1,2-vinyl bond content: about 85%) is dissolved, and then a cyclohexane solution containing 60 mmol of n-butyllithium is added and reacted at room temperature for 5 minutes, and immediately 40 mmol of n-butanol is added. The hydrogenation catalyst was obtained by adding and stirring.

[Production Example 1]
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.
After charging 10 parts by mass of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium is 0.08% by mass with respect to the mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by mass of styrene as a monomer ( A monomer concentration of 22% by mass) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to about 70 ° C.
Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 48 parts by mass of butadiene and 36 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 60 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) is added over about 3 minutes, and the reaction is carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. Got.
The resulting copolymer had a styrene content of 52% by mass and a styrene polymer block content of 16% by mass.
Next, 100 weight ppm of the hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.
After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated copolymer having a styrene polymer block (A) at both ends (hereinafter referred to as polymer 1) was obtained.
The hydrogenation rate of polymer 1 was 99%.

[Production Example 2]
A copolymer was obtained in the same manner as in Example 1, except that the amount of monomers and the like supplied to the reactor was changed.
The supply amount of n-butyllithium is 0.07% by mass, styrene supplied in the first stage is 6 parts by mass, butadiene supplied in the second stage is 54 parts by mass, styrene is supplied in 34 parts by mass, and three stages. Polymerization was carried out in the same manner except that the amount of styrene supplied to the eye was changed to 6 parts by mass.
Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (hereinafter referred to as polymer 2) having both ends at the styrene polymer block (A).
The properties of polymer 2 are shown in Table 1.

[Production Example 3]
Batch polymerization was performed in the same manner as in Production Example 1 to obtain a non-hydrogenated copolymer.
When the polymerization is completed, the living polymer is reacted with an equimolar amount of n-butyllithium used for the polymerization using 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine as a modifier. A modified copolymer was obtained.
The modification rate of the resulting modified copolymer was 80%.
Next, a hydrogenation reaction is carried out in the same manner as in Example 1 using a hydrogenation catalyst to obtain a modified hydrogenated copolymer (hereinafter referred to as polymer 3) having both ends at the styrene polymer block (A). It was.
The properties of polymer 3 are shown in Table 1.

[Production Example 4]
Batch polymerization was performed by the following method using the reactor used in Production Example 1.
A cyclohexane solution (concentration: 24% by mass) containing 8 parts by mass of butadiene was charged into the reactor.
Next, 0.08% by mass with respect to the mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor) and 0.10 mol of TMEDA with respect to 1 mol of n-butyllithium are added. And polymerized at 70 ° C. for 1 hour.
The obtained polymer was sampled and the vinyl bond content was analyzed and found to be 18%. Thereafter, a cyclohexane solution (concentration of 24% by mass) containing 44 parts by mass of butadiene and 36 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour.
Further, a cyclohexane solution containing 12 parts by mass of styrene (concentration of 24% by mass) was added and polymerized at 70 ° C. for 1 hour to obtain a non-hydrogenated copolymer.
The obtained non-hydrogenated copolymer has a styrene content of 48% by mass, a styrene polymer block content of 12% by mass, a vinyl bond content of the butadiene portion of 18% by mass, a weight average molecular weight of 170,000, and a molecular weight distribution. Was 1.1.
Next, a hydrogenation reaction is performed in the same manner as in Production Example 1, and one terminal is a styrene polymer block (A) and the other terminal is a hydrogenated polymer block of a diene polymer. A copolymer (hereinafter referred to as “polymer 4”) was obtained.
The properties of polymer 4 are shown in Table 1.

[Production Example 5]
The same operation as in Production Example 1 was carried out except that the intermediate product (non-hydrogenated copolymer) produced during production of Polymer 1 in Production Example 1 was not hydrogenated, and both ends were styrene polymer blocks ( A non-hydrogenated copolymer (polymer 5) of A) was obtained.
The properties of polymer 5 are shown in Table 1.

[Production Example 6]
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.
After charging 10 parts by mass of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium is 0.08% by mass with respect to the mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), TMEDA was added in an amount of 0.4 mol with respect to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) was added over about 3 minutes. Was allowed to react for 30 minutes while adjusting to about 70 ° C.
Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 17 parts by mass of butadiene and 11 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 14 parts by mass of butadiene and 14 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 11 parts by mass of butadiene and 17 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) is added over about 3 minutes, and the reaction is carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. Got.
The obtained copolymer had a styrene content of 58% by mass and a styrene polymer block content of 16% by mass.
The vinyl bond content of the conjugated diene part was 18%.
Next, a hydrogenation reaction was performed in the same manner as in Production Example 1 to obtain a hydrogenated copolymer (hereinafter referred to as “polymer 6”) having both ends at the styrene polymer block (A).
The hydrogenation rate of polymer 5 was 97%. When the peak temperature of tan δ was determined by measuring the viscoelastic spectrum, there were three of −24 ° C., −2 ° C., and 18 ° C.
The properties of polymer 6 are shown in Table 1.

[Production Example 7]
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.
After charging 10 parts by mass of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium is 0.08% by mass with respect to the mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), TMEDA was added in an amount of 0.4 mol with respect to 1 mol of n-butyllithium, and then a cyclohexane solution containing 15 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) was added over about 3 minutes. Was allowed to react for 30 minutes while adjusting to about 70 ° C.
Next, a cyclohexane solution containing 70 parts by mass of butadiene (monomer concentration: 22% by mass) was continuously supplied to the reactor at a constant rate over 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution containing 15 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) is added over about 3 minutes, and the reaction is carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. Got.
The resulting copolymer had a styrene content of 30% by mass and a styrene polymer block content of 30% by mass.
Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (hereinafter referred to as “polymer 7”) having both ends at the styrene polymer block (A).
The hydrogenation rate of polymer 7 was 97%.
When the viscoelastic spectrum was measured to determine the peak temperature of tan δ, one of −78 ° C. was present.
The properties of polymer 7 are shown in Table 1.

[Examples 1-8], [Comparative Examples 1-10]
The materials shown below were kneaded by the following method to produce an unvulcanized rubber composition and a vulcanized rubber composition.
Conjugated diene polymer-1: Toughden (registered trademark) T4850 manufactured by Asahi Kasei Co., Ltd. [Modification rate: 46% (having adsorptivity to silica column), weight average molecular weight = 820,000, styrene content = 40% by mass, Vinyl content = 45 mass%, crystallization peak temperature Tg. By DSC measurement. = -26 ° C., Oil (TDAE manufactured by H & R Co., Vivatec 500) content in all 150 parts by mass = 50 parts by mass]
Conjugated diene polymer-2: Toughden (registered trademark) F3420 manufactured by Asahi Kasei Co., Ltd. [Modification rate 80% (having adsorptivity to silica column), weight average molecular weight = 810,000, styrene content = 35 mass%, Vinyl content = 40% by mass, crystallization peak temperature Tg. By DSC measurement. = -28 ° C., Oil (TDAE, Vivatec 500 manufactured by H & R Co., Ltd.) content in all 125 parts by mass = 25 parts by mass]
Conjugated diene polymer-3: Toughden (registered trademark) T2000 manufactured by Asahi Kasei Co., Ltd. [non-modified, weight average molecular weight = 370,000, styrene content = 25 mass%, crystallization peak temperature Tg. = -65 ° C., content of oil (TDAE manufactured by H & R, Vivatec 500) in all 100 parts by mass = 0 part by mass]
Silica (Evonik Japan Co., Ltd., Ultrasil 7000GR, Nitrogen adsorption specific surface area: 175 m ² / g)
Polymer 1: Hydrogenated copolymer produced in Production Example 1 Polymer 2: Hydrogenated copolymer produced in Production Example 2 Polymer 3: Hydrogenated copolymer produced in Production Example 3 Polymer 4: Production Hydrogenated copolymer / polymer 5 produced in Example 4: Non-hydrogenated copolymer / polymer 6 produced in Production Example 5: Hydrogenated copolymer / polymer 7 produced in Production Example 6: produced in Production Example 7 Hydrogenated copolymer / resin 1: Neopolymer 120 (JXTG Energy Co., Ltd., C9 petroleum resin, softening point 120 ° C.)
Resin 2: Coumarone G-90 (manufactured by Nikkiso Chemical Co., Ltd., Coumarone resin, softening point 90 ° C.)
Resin 3: YS Resin PX1250 (Yasuhara Chemical Co., Ltd., terpene resin, softening point 125 ° C.)
・ Silane coupling agent (Si75, manufactured by Evonik Japan)
・ Extension oil (Hiva R, Vivatec 500)
・ Carbon black (Tokai Carbon Co., Ltd., Seast KH (N339))
・ Zinc flower (Mitsui Metal Mining Co., Ltd., Zinc flower No. 1)
・ Stearic acid and wax: (Onouchi Shinsei Chemical Co., Ltd., Sunnock)
・ Anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine)
・ Sulfur / vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide)
・ Vulcanization accelerator 2 (diphenylguanidine)

[Example 1]
According to the formulation shown in Table 2, kneading was carried out by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet.
Using a kneader (with an internal volume of 0.5 L) equipped with a temperature control device, as a first stage kneading, a conjugated diene polymer-1 (Asahi Kasei Corporation) under the conditions of a filling rate of 65% and a rotor rotation speed of 50 rpm ) Toughden (registered trademark) T4850 manufactured by 150 parts by mass, of which oil (TDAE manufactured by H & R, TDAE, Vivatec 500) content 50 parts by mass, silica, 25 parts by mass of polymer 1 (hydrogenated copolymer) and silane coupling agent And 100 parts by weight of conjugated diene polymer-1 and 5 parts by weight of extender oil (TDAE “Vivatec 500” manufactured by H & R) so that the total blended oil is 55 parts by weight. did.
Here, the blended oil is a generic term for oil and extender oil previously contained in the conjugated diene polymer.
At this time, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader to obtain a blend.
Next, as the second stage of kneading, after cooling the blend obtained above to room temperature, carbon black, zinc white, stearic acid, wax, and anti-aging agent are added, and kneaded for 3.5 minutes in the kneader. did. Also in this case, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader. The discharge temperature was controlled by measuring the temperature of each formulation discharged from the kneader after kneading.
Further, after cooling the blend obtained above to room temperature, the unvulcanized rubber composition was heated at 70 ° C. for 30 minutes using an oven, and then kneaded at 30 ° C. for 30 minutes as the third stage kneading. After second kneading, sulfur and a vulcanization accelerator were added, kneaded for 1.5 minutes and discharged at 105 ° C. to obtain an unvulcanized rubber composition.
Thereafter, the scorch resistance of the unvulcanized rubber was measured, and the unvulcanized rubber composition was further vulcanized and molded with a vulcanization press at 160 ° C. for 30 minutes to obtain a vulcanized rubber sheet.
The rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) of the vulcanized rubber sheet were evaluated.

[Example 2]
The same operation as in Example 1 was carried out except that the blending amount of the polymer 1 was changed to 4 parts by mass, and scorch resistance characteristics, rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) were evaluated.

Example 3
The same operation as in Example 1 was performed except that the blending amount of the polymer 1 was set to 10 parts by mass, and scorch resistance characteristics, rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) were evaluated.

Example 4
Except for blending 50 parts by mass of the polymer 1, the same operation as in Example 1 was performed to evaluate the scorch resistance property, the rolling resistance property, the wet grip property, and the steering stability (100% tensile stress).

Example 5
The same operation as in Example 1 was performed except that the polymer 2 was used instead of the polymer 1, and scorch resistance characteristics, rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) were evaluated.

Example 6
The same operation as in Example 1 was performed except that the polymer 3 was used instead of the polymer 1, and the scorch resistance property, the rolling resistance property, the wet grip property, and the steering stability (100% tensile stress) were evaluated.

Example 7
Other than using conjugated diene polymer-2 instead of conjugated diene polymer-1 and adding 17 parts by mass of extender oil ("Vivatec 500" manufactured by H & R) so that the total amount of the compounded oil is 42 parts by mass. The same operation as in Example 3 was performed, and the scorch resistance characteristics, rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) were evaluated.

Example 8
Instead of using conjugated diene polymer-1, conjugated diene polymer-3 is used, except that 32 parts by mass of extender oil ("Vivatec 500" manufactured by H & R) is blended so that the total blended oil is 32 parts by mass. The same operation as in Example 3 was performed, and the scorch resistance characteristics, rolling resistance characteristics, wet grip properties, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 1]
The same operation as in Example 1 was performed except that the amount of polymer 1 was changed to 0 part by mass, and scorch resistance, rolling resistance, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 2]
The same operation as in Example 1 was performed except that polymer 5 was used instead of polymer 1, and scorch resistance, rolling resistance, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the polymer 6 was used instead of the polymer 1, and the scorch resistance property, the rolling resistance property, and the steering stability (100% tensile stress) were evaluated.

[Comparative Example 4]
The same operation as in Example 7 was performed except that the polymer 1 was not used, and scorch resistance characteristics, rolling resistance characteristics, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 5]
The same operation as in Example 7 was performed except that the resin 1 was used instead of the polymer 1, and the scorch resistance property, the rolling resistance property, and the steering stability (100% tensile stress) were evaluated.

[Comparative Example 6]
The same operation as in Example 7 was performed except that the resin 2 was used instead of the polymer 1, and the scorch resistance characteristics, rolling resistance characteristics, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 7]
The same operation as in Example 7 was performed except that the resin 3 was used instead of the polymer 1, and the scorch resistance characteristics, the rolling resistance characteristics, and the steering stability (100% tensile stress) were evaluated.

[Comparative Example 8]
The same operation as in Example 8 was performed except that the polymer 1 was not used, and scorch resistance characteristics, rolling resistance characteristics, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 9]
The same operation as in Example 1 was performed except that polymer 4 was used instead of polymer 1, and scorch resistance, rolling resistance, and steering stability (100% tensile stress) were evaluated.

[Comparative Example 10]
The same operation as in Example 1 was performed except that polymer 7 was used instead of polymer 1, and scorch resistance, rolling resistance, and steering stability (100% tensile stress) were evaluated.

  The compounding compositions of Examples 1 to 8 and Comparative Examples 1 to 10 are shown in Table 2, and the evaluation results of these rolling resistance characteristics, wet grip characteristics, scorch resistance, and steering stability (100% tensile stress) are shown in Table 3. 4, 5 are shown.

From Tables 3, 4, and 5, it was found that the conjugated diene polymer composition of the present invention has a high balance between rolling resistance characteristics and wet grip properties, and is further excellent in scorch resistance and steering stability.
On the other hand, it turned out that what does not satisfy the specific requirements of this invention like Comparative Examples 1-10 is inferior to the balance of a rolling resistance characteristic and wet grip property, and scorch resistance and steering stability.

  The modified conjugated diene polymer composition of the present invention has industrial applicability as a tire tread and a tire material.

Claims (7)

A rubber component containing a conjugated diene polymer (I);
Silica-based inorganic filler (b),
A hydrogenated copolymer (c),
Is a conjugated diene polymer composition containing
The hydrogenated copolymer (c) is a hydrogenated non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit.
At least obtained by hydrogenating a polymer block (A) comprising a vinyl aromatic monomer unit and a non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit. Having one hydrogenated copolymer block (B),
Having polymer blocks (A) at both ends;
And it is a hydrogenated copolymer having the following characteristics (1) and (2):
Conjugated diene polymer composition.
(1) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more.
(2) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (c), the peak of loss tangent (tan δ) is attributed to the conjugated diene polymer (A) by differential scanning calorimetry (DSC). One exists only in the range from the crystallization peak temperature to below -10 ° C.   The conjugated diene polymer composition according to claim 1, wherein the non-hydrogenated random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit has a vinyl bond content of less than 40%. .   The conjugated diene polymer composition according to claim 1 or 2, wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is 40 to 60% by mass.   The content of the polymer block (A) composed of the vinyl aromatic monomer unit in the hydrogenated copolymer (c) is 0 to 60% by mass. The conjugated diene polymer composition described in 1.   The conjugated diene polymer composition according to any one of claims 1 to 4, further comprising carbon black.   The conjugated diene polymer composition according to any one of claims 1 to 5, which is used for a base tread.   A tire comprising a tread containing a crosslinked product of the conjugated diene polymer composition according to any one of claims 1 to 6.