JP2019031659A - Modified conjugated diene polymer composition and tire - Google Patents

Abstract

An object of the present invention is to provide a modified conjugated diene-based polymer composition having an excellent balance of rolling resistance characteristics, steering stability, and wet grip properties. A modified conjugated diene polymer having a weight average molecular weight Mw and a number average molecular weight Mn ratio of Mw / Mn less than 1.5 by gel permeation chromatography (GPC) and having adsorptivity to a silica column ( A modified conjugated diene-based polymer composition containing a rubber component containing (a) and an oil (b), wherein the density of the oil (b) exceeds 1.0 g / cm3. Polymer composition. [Selection diagram] None

Description

  The present invention relates to a modified 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 a tire with excellent fuel efficiency, the tread has a two-layer configuration of a cap tread on the ground contact surface side and a base tread on the opposite surface side, and as a rubber material constituting the tread, rolling resistance is lowered, In order to suppress energy loss of a tire, a method of using a rubber material capable of forming a crosslinked rubber having excellent rolling resistance characteristics is known.
In view of the growing demand for low fuel consumption for tires, a technique for improving the rolling resistance characteristics of the rubber material constituting the tread has been studied in order to obtain a tire with better fuel efficiency.

As a method for improving the rolling resistance characteristics of the rubber material, for example, a method using an inorganic filler such as silica is generally used.
However, it is known that when an inorganic filler such as silica is used, the storage elastic modulus, fracture resistance, wear resistance and the like are lowered. In order to improve this defect, a silane coupling agent is generally blended, but a sufficient effect has not yet been obtained.
In particular, the storage elastic modulus is an important rubber physical property. For example, when used for a tire tread or the like, if the storage elastic modulus is not sufficient, the rigidity is lowered and the steering stability is lowered. On the other hand, rolling resistance characteristics and steering stability are becoming increasingly important as the performance of automobiles increases.

  As a technique for improving the balance between rolling resistance characteristics and steering stability of a rubber material blended with an inorganic filler, for example, Patent Document 1 includes a reactive group for rubber and an adsorbing group for an inorganic filler in the same molecule. A technique of blending an additive comprising a compound having an aliphatic amine as an active ingredient is disclosed.

JP 2003-183445 A

However, when manufacturing a compound containing the predetermined additive described in Patent Document 1, it is necessary to add a predetermined additive to the material mixture that has been used conventionally. There is a problem of complication.
In addition, according to the technique described in Patent Document 1, although the steering stability of the composition is improved, only the rolling resistance characteristic is maintained, so when used as a material for the base tread portion, the rolling resistance characteristic and Regarding the balance between steering stability and wet grip performance, sufficient characteristics have not yet been obtained, and there is a problem that further improvement is necessary.

  Therefore, in view of the above-mentioned problems of the prior art, an object of the present invention is to provide a modified conjugated diene polymer composition having a high balance of rolling resistance characteristics, steering stability and wet grip properties. .

As a result of intensive studies in order to solve the above-described problems of the prior art, the present inventors have determined that a rubber component containing a modified conjugated diene polymer having a predetermined molecular weight distribution and an oil having a predetermined density are included. The present inventors have found that the conjugated diene polymer composition is highly excellent in the balance of rolling resistance characteristics, steering stability, and wet grip properties, and completed the present invention.
That is, the present invention is as follows.

[1]
The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5, and contains a modified conjugated diene polymer (A) having adsorptivity to a silica column. Rubber component to
Oil (b),
A modified conjugated diene polymer composition comprising a conjugated diene polymer having a density exceeding 1.0 g / cm ³ .
[2]
The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5, and contains a modified conjugated diene polymer (A) having adsorptivity to a silica column. Rubber component to
A silica-based inorganic filler;
Oil (b),
Modified conjugated diene polymer composition, wherein the oil (b) has a density of 1.0 g / cm ³ or more.
[3]
The modified conjugated diene polymer (A) is the modified conjugated diene polymer composition according to [1] or [2], wherein the modification rate is 60% by mass or more.
[4]
The modified conjugated diene polymer composition according to [1] or [3], further including a silica-based inorganic filler.
[5]
The modified conjugated diene polymer composition according to any one of [1] to [4], further containing carbon black.
[6]
The modified conjugated diene polymer composition according to any one of [1] to [5], which is used for a base tread.
[7]
A tire comprising a base tread containing a crosslinked product of the modified conjugated diene polymer composition according to any one of [1] to [6].

  According to the present invention, a modified conjugated diene polymer composition having an excellent balance of rolling resistance characteristics, steering stability, and wet grip properties 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.

[Modified Conjugated Diene Polymer Composition]
The modified conjugated diene polymer composition in the first embodiment is:
The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5, and contains a modified conjugated diene polymer (A) having adsorptivity to a silica column. Rubber component to
Oil (b) having a density exceeding 1.0 g / cm ³ ;
Containing.

In the modified conjugated diene polymer composition in the second embodiment, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5. A rubber component containing a modified conjugated diene polymer (a) having an adsorptive property of
A silica-based inorganic filler;
Oil (b) having a density of 1.0 g / cm ³ or more;
Containing.

(Modified conjugated diene polymer (I))
The rubber component used in the modified conjugated diene polymer composition of the present embodiment has a ratio Mw / Mn of weight average molecular weight Mw and number average molecular weight Mn by gel permeation chromatography (GPC) of less than 1.5, and silica. The modified conjugated diene copolymer (A) having adsorptivity to the system column is contained.
It is preferable that the Mw / Mn of the modified conjugated diene polymer (A) is less than 1.5 because the rolling resistance characteristics are improved because the number of free end chains is less than that of the Mw / Mn of 1.5 or more. The Mw / Mn of the modified conjugated diene polymer (A) is preferably 1.4 or less, more preferably 1.3 or less.
Mw / Mn of the modified conjugated diene polymer (A) can be controlled within the above numerical range by appropriately adjusting the polymerization conditions of the conjugated diene polymer.
In order to make the modified conjugated diene polymer (a) have adsorptivity to a silica column, it is effective to adjust the functional group and the molecular structure. For example, the modified conjugated diene polymer (a) having adsorptivity to a silica column may be a modified conjugated diene polymer having a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent. Coalescence is mentioned.
The rolling resistance characteristic of a tire is considered to be improved by improving the dispersion of the silica particles due to the interaction between the silica particles blended in the tire and the modified conjugated diene polymer. The inventor of the present application pays attention to the fact that the modified conjugated diene polymer interacting with the silica particles exhibits a property of adsorbing to the silica column, and the modified conjugated diene heavy polymer having a good balance between rolling resistance characteristics and steering stability. Set as requirement for coalescence composition.

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.
The term “having adsorptivity” in the present specification 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 modification rate of the modified conjugated diene polymer (A) contained in the rubber component used in the modified conjugated diene polymer composition of the present embodiment can be measured by the method described in the examples described later, and rolling. From the viewpoint of improving resistance characteristics and wet grip properties, it is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more.
The modification rate of the modified conjugated diene polymer (A) can be controlled within the above numerical range by appropriately controlling the amount of the modifier for the conjugated diene polymer before modification.

Although it does not specifically limit as a conjugated diene compound used in order to comprise a conjugated diene type polymer, 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. 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 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. These may be used alone or in combination of two or more.

The conjugated diene polymer may be a random copolymer or a block 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 block copolymer is not limited to the following, but for example, a 2 type block copolymer comprising 2 blocks, a 3 type block copolymer comprising 3 blocks, and a 4 type block comprising 4 blocks. A copolymer etc. are mentioned. For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. When expressed, it is represented by an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, or the like.
In the above equation, the boundaries of each block need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

The modified conjugated diene polymer, which is in a state after undergoing a modification step described later, is a hydrogenated modified conjugated diene heavy polymer obtained by converting all or part of the double bonds of the conjugated diene polymer to saturated hydrocarbons after the modification. It may be a coalescence.
In that case, heat resistance and weather resistance are improved, and deterioration of the product when processed at a high temperature can be prevented. As a result, it exhibits even better performance in various applications such as automotive applications.
More specifically, the hydrogenation rate (ie, “hydrogenation rate”) of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose, and is not particularly limited. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3 to 70%, more preferably 5 to 65%, and still more preferably 10 to 60%. The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, 30 % Or less is more preferable, and 20% or less is further preferable. The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).

  The amount of bound conjugated diene in the modified 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. More preferably. Moreover, the amount of bonded aromatic vinyl in the modified 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 is not particularly limited, but is preferably 10 to 75 mol%, and more preferably 25 to 65 mol%. When the vinyl bond content 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 modified conjugated diene polymer (a) is a copolymer of butadiene and styrene, a butadiene bond is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond amount (1,2-bond amount) in the unit can be determined.

  Low hysteresis when the microstructure (the amount of each bond in the modified conjugated diene copolymer (a)) is in the above range and the glass transition temperature of the copolymer 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 modified 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 copolymer is a butadiene-styrene copolymer, the method described in Kolthoff (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In a known method of decomposing a polymer and analyzing the amount of polystyrene insoluble in methanol, a block in which 30 or more aromatic vinyl units are chained is preferably 5% by mass or less, more preferably based on the total amount of the polymer. Is 3% by mass or less.

  In this embodiment, a conjugated diene polymer (modified conjugated diene polymer) having, as a functional group, a compound having a specific structure introduced by reaction at the polymerization active terminal is further hydrogenated in an inert solvent. In this way, all or part of the double bond can be converted to a saturated hydrocarbon. Hydrogenation may be performed on the conjugated diene copolymer before modification, or the modified conjugated diene copolymer after modification may be hydrogenated. By performing hydrogenation, heat resistance and weather resistance are improved, and deterioration of the product when processed at high temperature can be prevented. As a result, it exhibits even better performance in various applications such as automotive applications.

(Method for producing modified conjugated diene polymer (a))
The method for producing the modified conjugated diene polymer (a) is described below.
<Polymerization process>
The modified conjugated diene polymer (a) contained in the modified conjugated diene polymer composition of the present embodiment has a molecular structure branched from a nitrogen-containing epoxy substituent, or a nitrogen-containing alkoxysilane substituent. A preferred example is a modified conjugated diene polymer having a molecular structure branched from the starting point.
In such a modified conjugated diene polymer production method, it is preferable to carry out the polymerization step using, for example, a polyfunctional anionic polymerization initiator or a monofunctional anionic polymerization initiator as the 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, 1 , 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 is more preferably added such that the polyfunctional anionic polymerization initiator measured by GPC has a polystyrene-equivalent weight average molecular weight of 1,000 to 10,000.

  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, Thiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, Polyfunctional organic lithium such as 1,3,5-trilithio-2,4,6-triethylbenzene Beam compounds. 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 the Lewis bases, tertiary monoamine trimethylamine, triethylamine, tertiary diamine N, N, N ′, N′-tetramethylethylenediamine, and cyclic ether tetrahydrofuran, 2,2-bis (2-oxasolanyl). ) Propane is preferred.
The Lewis base may be used alone or in combination of two or more.
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.

In the polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer, the molar ratio of the polyvinyl aromatic compound to the organic lithium is in the range of polyvinyl aromatic compound / organic lithium = 0.01 to 1.0. It is preferable that it is adjusted as described above.
The greater the amount of polyvinyl aromatic compound used relative to the organic lithium, the greater the proportion of molecular chain ends to which functional groups are imparted by the modification reaction of the conjugated diene polymer described later, and the affinity and reactivity with silica particles. Thus, the balance between the low hysteresis loss and the wet skid resistance in the modified conjugated diene polymer composition of the present embodiment is improved, and the wear resistance is also improved.
On the other hand, when the amount of the polyvinyl aromatic compound used is smaller than that of the organic lithium compound, the processability in kneading the composition can be improved, and from this point of view, the amount is 1 per 1 mol of the organic lithium compound. It is preferable to make it 0.0 mol or less.
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 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 modified conjugated diene polymer composition of this embodiment using a conjugated diene polymer obtained by using a polyfunctional anionic polymerization initiator having a molecular weight distribution in this range has a low Mooney viscosity and low hysteresis. The resulting vulcanizate has a good balance between loss and wet skid resistance.

  The conjugated diene polymer before modification for obtaining the modified conjugated diene polymer (a) is obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using the polyfunctional anionic polymerization initiator described above. can get.

The conjugated diene polymer before modification or the modified conjugated diene polymer after modification obtained by the polymerization step may be appropriately hydrogenated.
The hydrogenation method is not particularly limited, and a known method can be used. As a particularly suitable hydrogenation method, a method of hydrogenation by blowing gaseous hydrogen into a polymer solution in the presence of a catalyst may be mentioned.
Catalysts include heterogeneous catalysts such as catalysts in which noble metals are supported on porous inorganic materials; catalysts in which salts such as nickel and cobalt are solubilized and reacted with organoaluminum, etc., catalysts using metallocenes such as titanocene, etc. And homogeneous catalysts. Among these, a titanocene catalyst is preferable from the viewpoint of selecting mild hydrogenation conditions. The hydrogenation of the aromatic group can be performed by using a noble metal supported catalyst.
Specific examples of catalysts for hydrogenating unsaturated double bonds based on conjugated diene compounds include, but are not limited to, (A) metals such as Ni, Pt, Pd, and Ru are carbon, silica, and alumina. , Supported heterogeneous hydrogenation catalyst supported on diatomaceous earth, (B) organic acid salt such as Ni, Co, Fe, Cr or transition metal salt such as acetylacetone salt and reducing agent such as organic aluminum And so-called Ziegler-type hydrogenation catalysts, so-called organometallic complexes such as (C) organometallic compounds such as Ti, Ru, Rh, and Zr. Examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-35381, Hydrogenation catalysts described in Japanese Patent Application Laid-Open No. 2-9041 and Japanese Patent Application Laid-Open No. 8-109219 can also be used. A preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.

  If allenes, acetylenes, and the like are contained as impurities in the conjugated diene compound that is a polymerization monomer, 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 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, 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 is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, the polymerization temperature is preferably 0 ° C. or higher, and the active terminal after completion of the polymerization. From the viewpoint of sufficiently ensuring the reaction amount of the modifier with respect to the temperature, 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, the manufacturing method of the conjugated diene polymer which has a polymerization active terminal at the time of using a monofunctional anionic polymerization initiator is demonstrated.
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. Etc. 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.

When the conjugated diene polymer before modification of the modified conjugated diene polymer (A) is produced using the monofunctional anionic polymerization initiator, the conjugated diene compound polymer or aromatic vinyl compound (co-polymer) is used. Although it will not specifically limit if it is a polymer, It is preferable that it is a (co) polymer 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 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, 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 the formula (1), R ₁₀ and R ₁₁ are each independently a 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 from the above.
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 the formula (2), R ₁₂ and R ₁₃ are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and the group consisting of aralkyl group having 6 to 20 carbon atoms It represents at least one selected from the above.
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 having 1 to 20 carbon atoms. X represents a hydrogen atom, a Cl atom, a Br atom, or an I atom.

In the formula (3), R ₁₅ and R ₁₆ are each independently a 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 from the above.
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 above formula (1), R ₁₀ and R ₁₁ are not limited to the following, but for example, methyl group, ethyl group, propyl group, butyl group, octyl group, cyclopropyl group, 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- Examples include ethylhexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine.
The compound represented by the formula (1) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
The compound represented by the formula (1) is a hysteresis loss reduction of the modified conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the modified conjugated diene polymer of the present embodiment, and will be described later. From the viewpoint of chain transfer reaction 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, Examples include 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane and 1,2,3,6-tetrahydropyridine.
The compound represented by the formula (1) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
The compound represented by the formula (1) is a hysteresis loss reduction of the modified conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the modified conjugated diene polymer of the present embodiment, and will be described later. From the viewpoint of chain transfer reaction control, piperidine, hexamethyleneimine, azacyclooctane, and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, and piperidine and hexamethyleneimine are more preferable. More preferably, it is piperidine.

In the formula (2), R ₁₄ preferably represents an alkyl group having 2 to 16 carbon atoms, more preferably a carbon number, from the viewpoints of reactivity and interaction with inorganic fillers such as carbon and silica. It represents 3 to 10 alkyl groups.
The compound represented by the formula (2) is not limited to the following compounds, but examples thereof include 3-chloro-dimethylpropan-1-amine, 3-chloro-diethylpropan-1-amine, and 3-chloro-dibutyl. Propan-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-methylphene Rupropan-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 having any one repeating unit of the following formulas (4) to (6), X represents a hydrogen atom.

When X in the formula (2) represents a hydrogen atom, the compound represented by the 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-di Ptyl-2-butenyl-1-amine, N, N-dihexyl-2-butenyl-1-amine, N, N-dioctyl-2-butenyl-1-amine, N, N- (di-2-ethyl Hexyl) -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-buteni -1-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 2-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- And methyl-2-butenyl) hexamethyleneimine and (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.
From the viewpoint of reducing the hysteresis loss of the modified conjugated diene polymer composition of the present embodiment, the compound represented by the formula (2) is N, N-dibutyl-2-butenyl 1-amine, 1- (2- Butenyl) 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′-tetraethyl Toluylenediamine, N, N, N ′, N′-tetrapropyltoluylenediamine, N, N-dimethylxylidine, N, N-diethylxylidine, N, N-dipropylxylidine, N, N-dimethyl Mesidine, N, N-diethylmesidine, (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 compounds. For example, n-butyllithium, sec-butyllithium, tert- Examples include butyl lithium, n-propyl lithium, and iso-propyl lithium.

  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. It is preferable that the organolithium compound represented by any one of the following general formulas (7) to (10) is included.

In the formula (7), R ₁₀ and R ₁₁ are each independently a 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 from the above.
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 the formula (8), R ₁₂ and R ₁₃ are each independently a 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 from the above.
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 having 1 to 20 carbon atoms.

In the formula (9), R ₁₅ and R ₁₆ are each independently a 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 from the above.
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 (10), R ₁₇ together with the nitrogen atom to form a cyclic structure, the number of carbon atoms in total represent 4-12 alkyl group, which may have an unsaturated bond or a branched structure in a portion thereof .
R ₁₈ represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.

In the above formula (7), R ¹⁰ and R ¹¹ are not limited to the following, but examples include methyl group, ethyl group, propyl group, butyl group, octyl group, silithium group, ethylpropyl An amino lithium group, an ethyl butyl amino lithium group, an ethyl benzyl amino lithium group, and a methyl phenethyl amino lithium group are mentioned.
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 an adjacent nitrogen atom, the organolithium compound represented by the formula (7) is as follows: For example, but not limited to, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6 -Tetrahydropyridinolithium. 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 having 1 to 20 carbon atoms, as described above.
The conjugated diene polymer preferably represents a conjugated diene polymer 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 2 carbon atoms from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. It is preferably an alkylene group having 16 carbon atoms, more 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, ( -(Ethylbenzylamino) -propyl) lithium, (3- (methylphenethylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, (5- (dibutylamino) -pentyl) lithium, (6 -(Dibutylamino) -hexyl) lithium, (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 having a repeating unit represented by the formulas (11) to (13), as the organolithium compound represented by the formula (8), Although not limited to the following, 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 , (4- (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 organolithium compound represented by the formula (8) is limited to the following. Although not intended, for example, (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneiminyl) propyl) lithium, (3- (heptamethyleneiminyl) propyl) lithium, (3- (octa Methyleneiminyl) propyl) lithium, (3- (1,3,3-trimethyl-6-azabicyclo [3.2.1] octanyl) propyl) lithium, (3- (1,2,3,6-tetrahydropyri) Dinyl) propyl) lithium, (2- (hexamethineleniminyl) ethyl) lithium, (4- (hexamethyleneleniminyl) butyl) lithium, (5- (hexamethy (Nyleneiminyl) pentyl) lithium, (6- (hexamethineleniminyl) hexyl) lithium, (10- (hexamethineleniminyl) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (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- Thenyl), and 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, 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 and N, N-dimethyl-m-toluidinolithium. N, N-dimethyl-p-toluidinolithium, N, N-diethyl-o-toluidinolithium, N, N-diethyl-m-toluidinolithium, N, N-diethyl-p-toluidi Nolithium, N, N-dipropyl-o-toluidinolithium, N, N-dipropyl-m-toluidinolithium, N, N-dipropyl-p-toluidinolithium, N, N-dibutyl-o- Toluidinolithium, N, N-dibutyl-m-toluidinolithium, N, N-dibutyl-p-toluidinolithium, o-piperidinotorenolithium, p-piperidinotorenolithium, o-pi Lizinotoluenolithium, 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 is mentioned.
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 “manufactured by FMC” AI-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.

  Before the polymerization step of the conjugated diene polymer, which is the state before the modification of the modified conjugated diene polymer (A), an organolithium compound having at least one nitrogen atom in the molecule is prepared in advance as the polymerization initiator described above. The method can be prepared by any known method.

  The organolithium compound having at least one nitrogen atom in the molecule represented by the formula (7) is obtained by, for example, reacting the compound represented by the formula (1) and the organolithium compound in a hydrocarbon solvent. To obtain. 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, for example, represented by the formula (2) when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms. A lithium amide compound is reacted with an alkyl dihalide represented by the following formula (A), and further reacted with an organolithium compound. It is obtained by.

In the 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 a carbon number. A 2-16 alkylene group, More preferably, a C3-C10 alkylene group is represented.
The compound represented by the formula (A) is not limited to the following, but examples thereof include 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 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 Is mentioned.
From the viewpoints of reactivity and safety, the compound represented by the formula (A) includes 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 the 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 organolithium compound having at least one nitrogen atom in the molecule represented by the formula (8) has R ₁₄ having a repeating unit represented by any one of the formulas (11) to (13). When it represents a conjugated diene polymer, 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 the 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 the 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 of the 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. This tends to facilitate the generation 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.

  The conjugated diene polymer before modification of the modified conjugated diene polymer (a) is the above-mentioned various polymerization initiators, preferably an organolithium compound having at least one nitrogen atom in the molecule, or at least one nitrogen atom. It is obtained by polymerizing using a conjugated diene compound using a polymerization initiator system containing a compound having an organic group and an organic lithium 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.

  In the polymerization step of the conjugated diene polymer before the modification of the modified conjugated diene polymer (a), a conjugated diene is obtained using a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound. In the case of performing polymerization in which the polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound, 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 portions linked by 30 or more tend to be reduced or eliminated, MSR (stress relaxation) 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 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. As a result, the aromatic vinyl compound can be randomly copolymerized with the conjugated diene compound, and the polar compound tends to be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. 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.

  The amount of bound conjugated diene in the conjugated diene polymer before modification of the modified conjugated diene polymer (a) is not particularly limited, but is preferably 50% by mass to 100% by mass, and more preferably 60% by mass to 80% by mass. It is more preferable that the amount is not more than mass%. Moreover, 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, and more preferably 20% by mass or more and 40% by mass or less. 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 can measure according to the method as described in the Example mentioned later.

  The amount of vinyl bonds in the conjugated diene bond unit is not particularly limited, but is preferably 10 mol% or more and 75 mol% or less, and more preferably 25 mol% or more and 65 mol% or less. 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 can measure by the method as described in the Example mentioned later.

The conjugated diene polymer before modification of the modified conjugated diene polymer (a) may be a random copolymer or a block 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. Is mentioned.
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.
The block copolymer is not limited to the following, for example, a 2-type block copolymer consisting of 2 blocks, a 3-type block copolymer consisting of 3 blocks, and a 4-type block copolymer consisting of 4 blocks. Coalescence is mentioned. For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. When expressed, it is represented by an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, or the like.
In the above equation, the boundaries of each block need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

By further hydrogenating the conjugated diene polymer obtained by the above-described production method in an inert solvent, all or part of the double bonds can be converted to saturated hydrocarbons. In that case, heat resistance and weather resistance are improved, and the product tends to be prevented from being deteriorated when processed at a high temperature. As a result, it exhibits even better performance in various applications such as automotive applications.
The hydrogenation rate of the unsaturated double bond based on the conjugated diene compound (also simply referred to as “hydrogenation rate”) can be arbitrarily selected according to the purpose and is not particularly limited. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3.0% or more and 70% or less, more preferably 5.0% or more and 65% or less, and more preferably 10% or more and 60%. More preferably, it is as follows. The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, 30 % Or less is more preferable, and 20% or less is further preferable. The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).

The hydrogenation method is not particularly limited, and a known method can be used. A suitable hydrogenation method includes a method of hydrogenating by blowing gaseous hydrogen into the polymer solution in the presence of a catalyst.
As the catalyst, for example, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic substance; a catalyst in which a salt such as nickel or cobalt is solubilized and reacted with organic aluminum or the like, or a metallocene such as titanocene is used. Examples thereof include homogeneous catalysts such as catalysts. Among these, a titanocene catalyst is preferable from the viewpoint of selecting mild hydrogenation conditions. The hydrogenation of the aromatic group can be performed by using a noble metal supported catalyst.
The hydrogenation catalyst is not limited to the following, but, for example, (1) a supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (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 and a reducing agent such as organic aluminum, (3) Ti, Ru, Examples include so-called organometallic complexes such as organometallic compounds such as Rh and Zr.
Furthermore, as the hydrogenation catalyst, for example, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, The hydrogenation catalysts described in JP-B-2-9041 and JP-A-8-109219 are also included.
A preferable hydrogenation catalyst includes a reaction mixture of a titanocene compound and a reducing organometallic compound.

  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.

When the microstructure (the amount of each bond in the modified 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 higher and −15 ° C. or lower, A more excellent 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.

  When the modified conjugated diene polymer (a) used in the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, is the number of blocks in which 30 or more aromatic vinyl units are linked? Or it is preferable that it is not. Specifically, when the copolymer is a butadiene-styrene copolymer, the method described in Kolthoff (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In a known method for decomposing a polymer and analyzing the amount of polystyrene insoluble in methanol, a block in which 30 or more aromatic vinyl units are chained is preferably 5.0% by mass or less based on the total amount of the polymer, More preferably, it is 3.0 mass% or less.

<Modification process>
After obtaining a conjugated diene polymer having a polymerization active terminal by the above-described method, a modified modifier is reacted with the polymerization active terminal and a modification step is performed, whereby a modified conjugated diene polymer (I) is obtained. ) Is obtained.
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]
First, examples of the compound having a nitrogen atom in the molecule and two or more epoxy groups (modifier) include a compound 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 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 an ether and / or a hydrocarbon group having 1 to 20 carbon atoms having a tertiary amine, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, or ether, 3 It is a C1-C20 hydrocarbon group which has at least 1 type of a primary amine, an epoxy, carbonyl, and a 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.

  Examples of the compound (modifier) having an alkoxy group bonded to a silyl group in the molecule and a nitrogen atom include compounds represented by general formula (15), general formula (16), and general formula (17). Can be mentioned.

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 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} , each is independent.

  The modifying agent 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-ethyl Imidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tri Butoxysilyl) 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- (tri Methoxysilyl) 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, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1 [3- (Dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxy Silyl) 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 modifying agent represented by the general formula (16) is not limited to the following, but for example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2- Silacyclopentane, 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- Silacyclopentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilyl) Propyl) -1-aza-2-silacyclopentane and the like.

  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 the formula (17), the modifying agent in the case where Y is represented by the formula (D) is not limited to the following, but examples include 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-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- Ethoxy-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-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-trimethyl) Silyl-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-tri Ethoxysilylpropyl)-[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-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-azacyclopentane) propyl]- 1,3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl)-[3- (1-ethoxy-2- Trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-diethoxy-1-aza-2-) Lacyclopentane) 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-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-Dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl (Lopyl)-[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-tri Ethoxysilylpropyl) -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bis Aminomethylcyclohexane, bis (3-triethoxysilylpropyl) -bis [3- (2,2-diethoxy-1-aza-2-si Cyclopentane) 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-) Zacyclopentane) 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) -diethylenetri Examples include amines.

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 more preferably an integer of 2 to 10. 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 of the conjugated diene polymer are not particularly limited, but are preferably reacted at 0 to 20 ° C. for 30 seconds or longer.

  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, more preferably an integer of 6 to 10. preferable.

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 a modified conjugated diene polymer, a deactivation agent, a neutralizing agent, and the like may be added to the polymer solution as necessary after the modification reaction.
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 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 having a molecular structure branched from a nitrogen-containing epoxy substituent as produced 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 ²³ and k have the same meaning as in the general formula (14).

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

  Examples of the modified conjugated diene polymer 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), The compound etc. which are shown to General formula (21) are mentioned.

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 the general formula (20), (Polym) is a polymer chain, and R ^{32 to} R ³⁶ , m, and n are as defined in the 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, 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 a carbon number of 1 to 20, R ⁶⁶ and R ⁷⁰ each independently represents an alkylene group having 1 to 20 carbon atoms, 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 is an integer of 1 to 10 Indicates. 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 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and i represents an integer of 1 to 10. When there are a plurality of Z ^{4 s} , they are independent of each other.

In the general formula (G), Z ⁵ represents 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 ^{5 s} , each is independent.

(Rubber components other than conjugated diene polymer (a))
The modified conjugated diene polymer composition of the present embodiment contains, in addition to the modified conjugated diene polymer (a) described above, other rubber-like polymers as rubber components as long as the characteristics of the present embodiment are satisfied. You may go out.
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.
Specifically, natural rubber, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene Examples thereof include styrenic elastomers such as block copolymers or hydrogenated products thereof, acrylonitrile-butadiene rubber or hydrogenated products 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-based 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 modified conjugated diene polymer composition of the present embodiment, the content of the modified conjugated diene polymer (A) in the rubber component is preferably 5 to 100% by mass, more preferably 5 to 75% by mass. More 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.

(Oil (b))
The modified conjugated diene polymer composition in the first embodiment contains an oil (b) having a density exceeding 1.0 g / cm ³ .
The modified conjugated diene polymer composition in the second embodiment includes an oil (b) having a density of 1.0 g / cm ³ or more.
Hereinafter, the oil may be referred to as a high density oil.
By containing a high-density oil (b), the modified conjugated diene polymer composition of this embodiment is improved in handling stability, rolling resistance characteristics, and wet grip properties.
The handling stability is improved by including a high density oil (b), which increases the density of the composition as compared with a modified conjugated diene polymer composition containing only an extender oil that has been conventionally used. This is thought to be due to increased rigidity. When high density oil was blended with such a concept, the effect of improving rolling resistance characteristics and wet grip properties of the modified conjugated diene polymer composition was also obtained.

The high-density oil (b) can be used to improve the processability of the modified conjugated diene polymer composition, as in the case of conventionally used extension oils. That is, since it can be added to the modified conjugated diene copolymer as an extending oil as necessary, the addition amount is not limited as long as the processability can be improved. The upper limit of the density of the high-density oil (b) is preferably 1.07 g / cm ³ or less, more preferably 1.03 g / cm ³ or less from the viewpoint of workability.

Examples of the high-density oil (b) include oils derived from vegetable oils, and examples include trade name “Vivamax 5000” manufactured by H & R.
The high-density oil (b) is added to the modified conjugated diene polymer (a) solution and mixed to remove an oil-extended polymer solution to obtain an oil-extended polymer. Alternatively, the modified polymer diene polymer (A) may be kneaded with a silica-based inorganic filler or the like with a kneader to obtain a rubber compound.

In addition, as long as the effects of the present invention are satisfied, a conventionally used extending oil may be added to the modified conjugated diene polymer (a) or may be blended into the modified conjugated diene polymer composition. . In this case, the high density oil (b) whether the density of the total of conventional extender oil is more than 1.0 g / cm ^3, may be adjusted to a density 1.0 g / cm ³ or more.
When the adjustment is performed, the upper limit of the total density of the high-density oil (b) and the extending oil is preferably 1.07 g / cm ³ or less, more preferably 1.03 g / cm ³ . For example, 100 parts by mass of the modified conjugated diene polymer (A), 5 parts by mass of a conventional extension oil having a density of 0.95 g / cm ³ and 30 parts by mass of a high density oil of 1.02 g / cm ³ are used. By adding a part, the total density can be adjusted to more than 1.0 g / cm ³ and 1.03 g / cm ³ or less.

Conventionally used extender oil has a density of less than 1.0 g / cm ³ in order to improve the processability (extrusion processability, etc.) of the modified conjugated diene polymer (A) and its rubber composition. These are added as necessary.
The method of adding the extending oil to the modified conjugated diene polymer (a) is not particularly limited, but the method of adding the extending oil to the polymer solution and mixing to remove the solvent from the oil-extended polymer solution. Is preferred.
Examples of the extending oil include aroma oil, naphthenic oil, paraffin oil, and the like. Among these, from the viewpoint of environmental safety, oil bleed prevention and wet grip characteristics, an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less by the IP346 method is preferable. Examples of the aroma substitute oil include RAE and the like in addition to TDAE and MES shown in Kautschuk Gummi Kunststoff 52 (12) 799 (1999).

  The addition amount of the high-density oil (B) or the extension oil is not particularly limited, but is usually 10 to 60 parts by mass in total with respect to 100 parts by mass of the modified conjugated diene polymer (A). ~ 37.5 parts by mass are preferred.

  As a method for obtaining the modified conjugated diene polymer (a) from the polymer solution for removing the solvent from the oil-extended polymer solution, a known method can be used. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. The method, the method of devolatilizing directly with a drum dryer etc. are mentioned.

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

The silica-based inorganic filler used in the modified conjugated diene-based polymer composition of the present embodiment is not particularly limited, and a known one can be used, but includes SiO ₂ or Si ₃ Al as a structural unit. Solid particles are preferable, and SiO ₂ or Si ₃ Al is more preferable as a 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 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 modified conjugated diene polymer composition of the present embodiment, the nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler is 100 to 300 m ² / g from the viewpoint of obtaining more excellent rolling resistance characteristics. It is preferable that it is 170-250 m < ² > / g.

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

(Carbon black)
The modified conjugated diene polymer composition of this embodiment preferably further contains carbon black with respect to the rubber component containing the modified conjugated diene polymer (I), and with respect to 100 parts by mass of the rubber component, What contains 0.5-100 mass parts of carbon black further is more preferable.
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 0.5% with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer from the viewpoint of developing rolling resistance characteristics due to the addition of the silica-based inorganic filler and from the viewpoint of extrusion processability. -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 modified 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 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)
In the modified conjugated diene-based polymer composition of the present embodiment, a silane coupling agent is preferably added in a form in which a silica-based inorganic filler is blended.
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. Among them, bis- [3- (triethoxysilyl) -propyl] -disulfide, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik] Degussa: Si363], Momentive NXT-Z30, NXT-Z45, NXTZ60, silane coupling agent containing a mercapto group such as NXT silane, bis- [3- (triethoxysilyl) -propyl]- Tetrasulfide is preferable because of its high reinforcing effect. These silane coupling agents can be used singly or in combination of two or more.
0.1-30 mass parts is preferable with respect to 100 mass parts of silica type inorganic fillers mentioned above, as for the compounding quantity of a silane coupling agent, 0.5-20 mass parts is more preferable, and 1-15 mass parts is. Further preferred. 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 modified 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.
The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. 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 modified conjugated diene polymer. Further preferred.
If the blending amount of the rubber softener exceeds 100 parts by mass with respect to 100 parts by mass of the rubber component, bleeding out tends to occur, and the composition surface may become sticky.

(Kneading method and other additives)
In producing the modified conjugated diene polymer composition of this embodiment, the modified conjugated diene polymer (A) and other rubber-like polymers, high-density oil (B), silica-based inorganic filler, carbon, if desired. The method of mixing additives such as black and other fillers, silane coupling agents, and rubber softeners 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 modified conjugated diene polymer (a) and various compounding agents at a time and a method of mixing in multiple times can be applied.

The modified 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 modified 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 amount of the vulcanization accelerator 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 modified conjugated diene polymer (A). .

The modified conjugated diene-based polymer composition of the present embodiment includes other softeners and fillers other than those described above, as well as heat resistance stabilizers, antistatic agents, and weather resistance, as long as the purpose of the present embodiment is not impaired. Various additives such as a stabilizer, an anti-aging agent, a colorant, 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 modified conjugated diene polymer composition of this embodiment is suitable for a base tread, and is suitable for a tire application including a base tread containing a crosslinked product of the modified conjugated diene polymer of this embodiment.
That is, a tire can be manufactured by manufacturing a base tread using the modified conjugated diene polymer composition of the present embodiment, bonding together with other members, and heating and pressing using a tire molding machine. it can.
By using the modified conjugated diene polymer composition of the present embodiment, a tire excellent in the balance of rolling resistance characteristics and steering stability can be produced.

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, the structure and physical properties of the polymers were measured by the methods shown below.

(Physical property 1) Amount of bound styrene Using a modified conjugated diene polymer as a sample, 100 mg of the sample was made up to 100 mL with chloroform and dissolved to prepare a measurement sample.
The amount of bound styrene (% by mass) with respect to 100% by mass of the modified conjugated diene polymer as a sample was measured by the amount of absorption at the ultraviolet absorption wavelength (around 254 nm) by the phenyl group of styrene (Spectra manufactured by Shimadzu Corporation). Photometer “UV-2450”).

(Physical property 2) Microstructure of butadiene part (1,2-vinyl bond amount)
Using the modified conjugated diene polymer as a sample, 50 mg of the sample was dissolved in 10 mL of carbon disulfide to prepare a measurement sample.
Using a solution cell, the infrared spectrum is measured in the range of 600 to 1000 cm −1, and the method of Hampton is determined by the absorbance at a predetermined wave number (the method described in RR Hampton, Analytical Chemistry 21, 923 (1949)). The microstructure of the butadiene portion, that is, the 1,2-vinyl bond amount (mol%) was determined (Fourier transform infrared spectrophotometer “FT-IR230” manufactured by JASCO Corporation).

(Physical property 3) Molecular weight Using a modified conjugated diene polymer as a sample, a GPC measuring apparatus in which three columns using polystyrene gel as a filler were connected, a chromatogram was measured, and a calibration curve using standard polystyrene Based on the above, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined.
The eluent used was THF containing 5 mmol / L triethylamine. 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.
An RI detector (trade name “HLC8020” manufactured by Tosoh Corporation) was used under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 0.6 mL / min.
10 mg of a sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 20 μL of the measurement solution was injected into a GPC measurement device and measured.

(Physical property 4) Mooney viscosity Using a modified conjugated diene polymer as a sample, Mooney viscometer (trade name “VR1132” manufactured by Ueshima Seisakusho Co., Ltd.) is used, and Mooney viscosity is measured using an L-shaped rotor in accordance with JIS K6300. did.
The measurement temperature was 110 ° C. when a conjugated diene polymer was used as a sample, and 100 ° C. when a modified conjugated diene polymer was used as a sample.
First, after preheating the sample at the test temperature for 1 minute, the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML _{(1 + 4)} ).

(Physical property 5) Modification rate Using a modified conjugated diene polymer as a sample, 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.
The measurement is performed under the following measurement conditions, and the results are shown in Tables 1 and 2 below.
-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 6) Steering Stability Viscoelastic parameters were measured in a torsion mode using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments.
Each measured value was indexed with Comparative Examples 1 to 10 and 12 to 17 as 100 for each table.
The storage elastic modulus G ′ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an indicator of steering stability. The larger the value, the better the steering stability.

(Physical property 7) 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 was indexed with Comparative Examples 1 to 10 and 12 to 17 as 100 for each table.
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 8) Wet grip property Viscoelasticity parameters were measured in a torsion mode using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments.
Each measured value was indexed with Comparative Examples 1 to 10 and 12 to 17 as 100 for each table.
Tan δ measured at a frequency of 10 Hz and a strain of 1% at 0 ° C. was used as an index of rolling resistance characteristics (low fuel consumption). The larger the value, the better the rolling resistance characteristic.
The composition of a commercially available oil-extended modified conjugated diene polymer was specified by separating the oil by the following oil extraction method.
By measuring the density of the oil extracted by this method, it was compared with the modified conjugated diene polymer of this embodiment.
<Oil extraction method>
Soxhlet extraction method (acetone) is used as a method for extracting oil from oil-extended modified conjugated diene polymers. The oil contained in oil-extended modified conjugated diene polymers is dissolved in acetone and extracted, and then acetone is evaporated. The remaining oil was separated.
Using a soxhlet extractor, a container with a heater and solvent at the bottom, a tube with filter paper containing a sample of an oil-extended conjugated diene polymer in the middle, and a device with a cooling pipe at the top By the extraction method (acetone), oil was extracted from the oil-extended modified conjugated diene polymer using acetone.
When the solvent container is heated, acetone evaporates and is cooled in the uppermost cooling pipe, dripped onto the oil-extended modified conjugated diene polymer, dissolves a small amount of the solvent soluble component, and then returns to the solvent container. Since the solvent-soluble component has a boiling point higher than that of the solvent, by repeating this cycle, the solvent-soluble component is gradually concentrated in the solvent container, and the solvent-insoluble component remains in the filter paper. Since the refluxing solvent does not contain the target component, it was efficiently extracted with a relatively small amount of solvent without being saturated.
The Soxhlet extraction method (acetone) can extract more than 99% of the oil, but the oil extracted by the Soxhlet extraction method can be used when adding acetone, evaporating acetone, refining, and deodorizing. The temperature was raised many times, but at this time, in order to avoid changing the state of the oil, the temperature was not raised (100 ° C. or higher) during Soxhlet extraction.

[Production Example 1-1]
An autoclave having an internal volume of 10 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were previously removed. 777 g of 1,3-butadiene, 273 g of styrene, 4800 g of cyclohexane, 2,2 as a polar substance -0.81 g of bis (2-oxolanyl) propane was put into the reactor, and the reactor internal temperature was kept at 42 ° C.
As a polymerization initiator, a cyclohexane solution containing 9.5 mmol of n-butyllithium was supplied to the reactor.
After the polymerization reaction started, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 73 ° C. Two minutes after reaching the peak of the reaction temperature, 4.3 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to the reactor, and the mixture was stirred at 72 ° C. for 2 minutes to carry out a modification reaction. H &R's product name “Vivamax 5000” as a high-density oil was added to 30 g (30 parts by mass), mixed with a mixer, mixed with a mixer, and then mixed with 2.1 g of an antioxidant (BHT) in this polymerization solution. After adding the solvent, the solvent was removed by steam stripping, followed by drying with a dryer to obtain a modified conjugated diene polymer (sample α1) having a molecular structure branched from a nitrogen-containing epoxy group substituent.

[Production Example 1-2]
In Production Example 1-1, instead of adding the product name “Vivamax 5000” manufactured by H & R as a high-density oil to 100 g of the polymer, 7 g (7 parts by mass) of the product name “Vivamax 5100” manufactured by H & R is used. Added. The other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α2).

[Production Example 1-3]
In Production Example 1-1, instead of adding a high-density oil product name “Vivamax 5000” to 100 g of the polymer, the extension oil H & R product name “Vivatec 500” is 30 g (30 parts by mass). Was added as follows. Other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α3).

[Production Example 1-4]
In Production Example 1-1, instead of adding a high-density oil H & R trade name “Vivamax 5000” to 100 g of the polymer, the extension oil H & R trade name “Vivatec 500” is 7 g (7 parts by mass). Was added as follows. The other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α4).

[Production Example 1-5]
In Production Example 1-1, instead of adding a high-density oil product name “Vivamax 5000” to 100 g of the polymer, 30 g (30 parts by mass) of the oil product name “Nytex 4700” made by extension oil Minas is used. Was added as follows. The other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α5).

[Production Example 1-6]
In Production Example 1-1, instead of adding a high-density oil product name “Vivamax 5000” to 100 g of the polymer, Toray Dow Corning Co., Ltd. product name “SH510” was used as a modified silicone oil. It added so that it might become 7g (7 mass parts). The other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α6).

[Production Example 1-7]
In Production Example 1-1, a high-density oil product name “Vivamax 5000” manufactured by H & R Co. was not added. The other conditions were the same as in Production Example 1-1 to obtain a modified conjugated diene polymer (sample α7).

[Production Example 2-1]
Using an autoclave with an internal volume of 10 L and a jacket as a reactor, cyclohexane and normal butyl lithium were added to the reactor and washed, and then purged with nitrogen to obtain 4583 g of cyclohexane, 47.4 g of divinylbenzene, 1 1,3 butadiene was added and the temperature in the reactor was maintained at 40 ° C., and then 341 g of n-butyllithium solution was added and reacted for 90 minutes to raise the temperature in the reactor to 80 ° C. Thereafter, the mixture was allowed to cool in the reactor for 2 hours to prepare a polyfunctional catalyst.
The n-butyllithium solution of the raw material was a solution having a weight mixing ratio of n-butyllithium / cyclohexane of 20/80. The divinylbenzene contained m-divinylbenzene, p-divinylbenzene, ethylbenzene and the like, and a divinylbenzene mixture (manufactured by Nippon Steel Chemical Co., Ltd.) having a divinylbenzene concentration of 57% by mass was used.
Using an autoclave having an internal volume of 40 L and a jacket as a reactor, cyclohexane and normal butyl lithium were added to the reactor and washed, and then nitrogen substitution was performed. In the reactor, 20915 g of cyclohexane, 779 g of styrene, After adding 4.5 g of 2,2-bis (2-oxolanyl) propane and 2221 g of butadiene as polar compounds and maintaining the temperature in the reactor at 45 ° C., 204 g of polyfunctional anion initiator was added and the polymerization reaction was started. The peak temperature in the reactor reached 83 ° C. and the polymerization reaction was completed. One minute after the completion of the polymerization reaction, 5.6 g of 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine as a modifier was fed into the reactor at an addition rate of 5 seconds or less. A modification reaction was performed, and a product name “Vivamax 5000” manufactured by H & R as a high-density oil was added to 100 g of the polymer so as to be 10 g (10 parts by mass), mixed with a mixer, mixed with a mixer, and then steamed. The solvent was removed by ripping and vacuum drying was performed to obtain a modified conjugated diene polymer (sample β1) having a molecular structure branched from a nitrogen-containing alkoxysilane substituent. As the n-butyllithium solution, a solution having a weight mixing ratio of 20/80 of n-butyllithium / cyclohexane was used.

[Production Example 2-2]
In Production Example 2-1, instead of adding the high-density oil H & R trade name “Vivamax 5000” to 100 g of the polymer, the extension oil H & R trade name “Vivatec 500” becomes 10 g (10 parts by mass). A modified conjugated diene polymer (sample β2) was obtained by performing the same operation as in Production Example 2-1, except that the addition was performed as described above.

[Production Example 3-1]
An autoclave having an internal volume of 5 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were previously removed. 265 g of 1,3-butadiene, 93 g of styrene, 2030 g of cyclohexane, 2,2 as a polar substance -3.8 mmol of bis (2-oxolanyl) propane was put into the reactor, and the temperature inside the reactor was kept at 50 ° C. As a polymerization initiator, a cyclohexane solution of 1-lithiopiperidine (5.10 mmol) obtained by reacting piperidine (5.10 mmol) and n-butyllithium (5.10 mmol) was supplied to the reactor. After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the exotherm caused by the polymerization, and the final temperature inside the reactor reached 78 ° C.
Two minutes after the peak of the reaction temperature was reached, 0.587 mmol of tris (3-trimethoxysilylpropyl) amine was added to the reactor and a denaturation reaction was carried out for 5 minutes. The name “Vivamax 5000” was added to 30 g (30 parts by mass), mixed with a mixer, mixed with a mixer, and then antioxidant (2,6-di-tert-butyl-4-hydroxytoluene; BHT). After adding 1.0 g, the solvent is removed by steam stripping, the drying treatment is performed by a dryer, and the modified conjugated diene polymer having a molecular structure branched from the nitrogen-containing alkoxysilane substituent (sample γ1) Got.

[Production Example 3-2]
In Production Example 3-1, instead of adding the high-definition oil H & R trade name “Vivamax 5000” to 100 g of the polymer, the extended oil H & R trade name “Vivatec 500” is 30 g (30 parts by mass). Was added as follows. The other conditions were the same as in Production Example 3-1, and a modified conjugated diene polymer (sample γ2) was obtained.

[Production Example 4-1]
Using an autoclave with an internal volume of 5 L (L / D: 3.4) and a temperature-controllable autoclave equipped with a stirrer and a jacket, it may interfere with the polymerization reaction existing in the reactor with 1995 g of normal hexane. For neutralization of impurities, n-butyllithium was put into the reactor, stirred at 70 ° C. for 5 minutes, cooled to room temperature, the solution was taken out, and the reactor was emptied.
Next, 1670 g of normal hexane from which impurities were previously removed, 83 g of styrene, 236 g of 1,3-butadiene, and 3.50 mmol of 2,2-bis (2-oxolanyl) propane as a polar substance were placed in the reactor. Was 50 ° C., 3.59 mmol of n-butyllithium was added as a polymerization initiator to initiate polymerization.
Immediately after the start of polymerization, the temperature in the reactor increased and reached a peak temperature, which was 81 ° C. When a decrease in temperature was confirmed, 0.38 mmol of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine adjusted to 50 ° C. was added as a coupling agent, and the mixture was further stirred for 10 minutes. The stirring speed at this time was 200 rpm. The coupling agent was added 2 minutes after the peak temperature was reached.
2.92 mmol of ethanol was added as a polymerization terminator to stop the reaction, and a modified conjugated diene polymer-containing polymer solution was obtained.
To the resulting polymerization solution, 0.64 g of 2,6-di-tert-butyl-4-hydroxytoluene as an antioxidant, and a product name “Vivamax 5000” manufactured by H & R, a high-density oil with respect to 100 g of the polymer. 25.7 g (25.7 parts by mass), H & R product name “Vivatec 500” as an extension oil was added to 4.3 g (4.3 parts by mass), mixed with a mixer, and then steam stripped. After removing the solvent and vacuum drying, a modified conjugated diene copolymer (sample θ1) having a molecular structure branched from a nitrogen-containing alkoxysilane substituent was obtained.

[Production Example 4-2]
In Production Example 4-1, the product name “Vivatec 500” manufactured by H & R was not added as the extension oil, and the product name “Vivamax 5000” manufactured by H & R, a high-density oil, was added to 30 g (30 parts by mass). Other conditions were the same as in Production Example 4-1, and a modified conjugated diene polymer (sample θ2) was obtained.

[Production Example 4-3]
In Production Example 4-2, the high-density oil H & R trade name “Vivamax 5000” was not added, and the high-density oil H & R trade name “Vivamax 5100” was added to 7 g (7 parts by mass). The other conditions were the same as in Production Example 4-2 to obtain a modified conjugated diene polymer (sample θ3).

[Production Example 4-4]
In Production Example 4-1, the product name “Vivamax 5000” manufactured by H & R, a high-density oil, was not added, and the product name “Vivatec 500” manufactured by H & R, an extended oil, was added to 30 g (30 parts by mass). Other conditions were the same as in Production Example 4-1, and a modified conjugated diene polymer (sample θ4) was obtained.

[Production Example 4-5]
In Production Example 4-2, the product name “Vivatec 500” manufactured by H & R was added as an extending oil to 7 g (7 parts by mass) without using the product name “Vivamax 5000” manufactured by H & R, which is a high-density oil. Other conditions were the same as in Production Example 4-2, and a modified conjugated diene polymer (sample θ5) was obtained.

[Production Example 4-6]
In the manufacture example 4-4, the addition amount of H & R company brand name "Vivatec500" of extension oil was added so that it might become 4.3g (4.3 mass parts). The other conditions were the same as in Production Example 4-4 to obtain a modified conjugated diene polymer (sample θ6).

[Production Example 5-1]
In Production Example 1-1, the amount of tetraglycidyl-1,3-bisaminomethylcyclohexane added was 1.46 mmol. For other conditions, the same operation as in Production Example 1-1 was performed to obtain a modified conjugated diene polymer (sample ε1).

[Production Example 5-2]
In Production Example 5-1, instead of adding the product name “Vivamax 5000” manufactured by H & R of high-density oil, 30 g (30 parts by mass) of the product name “Vivatec 500” manufactured by H & R of extension oil was added. Other conditions were the same as in Production Example 5-1, and a modified conjugated diene polymer (sample ε2) was obtained.

[Production Example 6-1]
In Production Example 1-1, the amount of tetraglycidyl-1,3-bisaminomethylcyclohexane added was 3.25 mmol. For other conditions, the same operation as in Production Example 1-1 was performed to obtain a modified conjugated diene polymer (sample σ1).

[Production Example 6-2]
In Production Example 6-1, instead of adding the product name “Vivamax 5000” manufactured by H & R Co., which is a high-density oil, 30 g (30 parts by mass) of the product name “Vivatec 500” manufactured by H & R Co., Ltd. was used. The other conditions were the same as in Production Example 6-1 to obtain a modified conjugated diene polymer (sample σ2).

[Production Example 6-3]
In Production Example 6-2, the trade name “Vivatec 500” manufactured by H & R Co., Ltd., was not added. For other conditions, the same operation as in Production Example 6-2 was performed to obtain a modified conjugated diene polymer (sample σ3).

  Production conditions of modified conjugated diene polymers produced in Production Examples 1-1 to 6-3, bound styrene content, 1,2-vinyl bond content, Mooney viscosity, modification rate, weight average molecular weight (Mw), number average molecular weight Tables 1 and 2 show (Mn) and the Mw / Mn ratio.

[Examples 1-17], [Comparative Examples 1-17]
The materials shown below were kneaded by the following method to produce an unvulcanized rubber composition and a vulcanized rubber composition.
Modified conjugated diene polymer: Samples α1 to α6, β1, β2, γ1, γ2, θ1 to θ6, ε1, ε2, and σ1 to σ3 (modified conjugated diene produced in Production Examples 1-1 to 6-3) Polymer)
Silica (Evonik Japan Co., Ltd., Ultrasil 7000GR, Nitrogen adsorption specific surface area: 175 m ² / g)
・ Silane coupling agent (Si75, manufactured by Evonik Japan)
High density oil 1 (H & R, Vivamax 5000, density 1.02 g / cm ³ )
・ High-density oil 2 (H & R, Vivamax 5100, density 1,01 g / cm ³ )
・ Extension oil 1 (H & R, Vivatec 500, density 0.95 g / cm ³ )
・ Modified silicone oil (Phenyl group-modified dimethyl silicone oil, SH510, density 0.99 g / cm ³ manufactured by Toray Dow Corning Co., Ltd.)
Extension oil 2 (Ninas, Nytex 4700, density 0.94 g / cm ³ )
・ Carbon black (Tokai Carbon Co., Ltd., Seast KH (N339))
・ Adhesive resin 1 (hydrogenated cyclopentadiene “DCPD” manufactured by UNS Chemical Co., Ltd.)
・ Adhesive resin 2 (modified terpene phenol resin “T160” manufactured by Yashara Chemical Co., Ltd.)
・ 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 3, 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, under the conditions of a filling rate of 65% and a rotor rotational speed of 50 rpm, a modified conjugated diene polymer (sample α1), The mixture was kneaded for 4 minutes using silica and a silane coupling agent. At this time, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader to obtain a blend. The density of the entire blended oil (high-density oil, high-density oil, extension oil, and modified silicone oil) used at this time was 1.02 g / cm ³ .
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 unvulcanized rubber composition was vulcanized and molded with a vulcanizing press at 160 ° C. for 20 minutes to obtain a vulcanized rubber sheet. The rolling resistance characteristics, steering stability, and wet grip properties of the vulcanized rubber sheet were evaluated.

[Example 2]
As the modified conjugated diene-based polymer, 110 parts by mass of “sample β2” produced in Production Example 2-1 was used instead of “Sample α1” produced in Production Example 1-1. Sample β2 contains 10 parts by mass of high-density oil 1. The same operation as in Example 1 was performed except that 20 parts by mass of the high-density oil 1 was blended so that the blended oil amount including the high-density oil content in the sample β2 was 30 parts by mass. Stability and wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 3
As the modified conjugated diene polymer, the same operation as in Example 1 was performed except that “Sample γ1” produced in Production Example 3-1 was used instead of “Sample α1” produced in Production Example 1-1. Rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Sample γ1 contains 30 parts by mass of high-density oil 1.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 4
As the modified conjugated diene polymer, the same operation as in Example 1 was performed except that “Sample θ1” produced in Production Example 4-1 was used instead of “Sample α1” produced in Production Example 1-1. Rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Sample γ1 contains 25.7 parts by mass of high-density oil 1 and 4.3 parts by mass of extended oil, for a total of 30 parts by mass.
The density of the entire blended oil used at this time was 1.01 g / cm ³ .

Example 5
As a modified conjugated diene polymer, 107 parts by mass of “Sample α2” produced in Production Example 1-2 instead of “Sample α1” produced in Production Example 1-1, 20 parts by mass of silica and silane were used. The same operation as in Example 1 was carried out except that the coupling agent blending amount was changed to 1.6 parts by mass and no carbon black was blended, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample α2 contains 7 parts by mass of the extending oil 2.
The density of the entire blended oil used at this time was 1.01 g / cm ³ .

Example 6
In Example 1, 40 parts by mass of high-density oil 1 is blended so that the amount of blended oil is 70 parts by mass including the high-density oil in sample α1, and 200 parts by mass of silica is blended with silane coupling. The same operation as in Example 1 was performed except that the compounding amount of the agent was changed to 16 parts by mass and no carbon black was added, and the rolling resistance characteristic, the steering stability, and the wet grip property were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 7
In Example 1, except that 130 parts by mass of “Sample θ2” manufactured in Preparation Example 2-2 was used instead of “Sample α1” manufactured in Preparation Example 1-1 as the modified conjugated diene polymer. The same operation as in Example 1 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample θ2 contains 30 parts by mass of the extending oil 1.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 8
In Example 1, as a modified conjugated diene-based polymer, 107 parts by mass of “sample θ3” produced in Production Example 4-3 instead of “Sample α1” produced in Production Example 1-1 was used, and the silica compounding amount was changed. The same operation as in Example 1 was carried out except that 20 parts by mass and the silane coupling agent compounding amount were changed to 1.6 parts by mass and no carbon black was added, and rolling resistance characteristics, steering stability, and wet grip Sex was evaluated. The sample θ3 contains 7 parts by mass of the extending oil 2.
The density of the entire blended oil used at this time was 1.01 g / cm ³ .

Example 9
In Example 7, 40 parts by mass of high density oil 1 is blended so that the amount of blended oil is 70 parts by mass including the high density oil in sample θ2, and 200 parts by mass of silica and silane coupling are blended. The same operation as in Example 7 was carried out except that the amount of the agent was changed to 16 parts by mass and no carbon black was added, and the rolling resistance characteristics, the steering stability, and the wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 10
In Example 1, except that 130 parts by mass of “Sample ε1” produced in Production Example 5-1 was used instead of “Sample α1” produced in Production Example 1-1 as the modified conjugated diene polymer. The same operation as in Example 1 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample ε1 contains 30 parts by mass of the extending oil 1.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 11
In Example 1, except that 130 parts by mass of “Sample σ1” produced in Production Example 6-1 was used instead of “Sample α1” produced in Production Example 1-1 as the modified conjugated diene polymer. The same operation as in Example 1 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample σ1 contains 30 parts by mass of the extending oil 1.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 12
In Example 1, 2 parts by mass of adhesive resin 1 (hydrogenated cyclopentadiene “DCPD” manufactured by UNS Chemical Co., Ltd.) and 3 masses of adhesive resin 2 (modified terpene phenol resin “T160” manufactured by Yasuhara Chemical Co., Ltd.) The same operation as in Example 1 was carried out except that the parts were used, and the rolling resistance characteristics, the steering stability, and the wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 13
In Example 1, as a modified conjugated diene polymer, 100 parts by mass of “sample σ3” produced in Production Example 6-3 instead of “Sample α1” produced in Production Example 1-1 was used, and high-density oil 1 40 parts by mass, and the same operation as in Example 1 except that the compounding amount of silica was 100 parts by mass and the compounding amount of the silane coupling agent was 8 parts by mass, rolling resistance characteristics, steering stability, and Wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 14
As a modified conjugated diene polymer, 100 parts by mass of “Sample α7” produced in Production Example 1-7 is used instead of “Sample α1” produced in Production Example 1-1, and 30 parts by mass of high-density oil 1 is blended. Except for the above, the same operation as in Example 1 was performed, and the rolling resistance characteristic, the steering stability, and the wet grip property were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 15
As the modified conjugated diene polymer, 104.3 parts by mass of the “sample θ6” manufactured in the manufacture example 4-6 instead of the “sample α1” manufactured in the manufacture example 1-1 is used, and the extending oil 1 in the sample θ6 is used. The same operation as in Example 1 was performed except that 25.7 parts by mass of the high-density oil 1 was blended so that the blended oil amount was 30 parts by mass, and the rolling resistance characteristics, steering stability, and Wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

Example 16
In Example 14, the blending amount of the high-density oil 2 instead of the high-density oil 1 is 7 parts by mass, the silica blending amount is 20 parts by mass, the silane coupling agent blending amount is 1.6 parts by mass, and carbon black The same operation as in Example 1 was carried out except that zinc white, stearic acid, wax, and anti-aging agent were not blended, and the rolling resistance characteristics, steering stability, and wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.01 g / cm ³ .

Example 17
In Example 14, the blending amount of the high-density oil 1 is blended by 70 parts by mass, the silica blending amount is 200 parts by mass, the silane coupling agent blending amount is 16 parts by mass, and further carbon black, zinc white, stearic acid, wax. The same operation as in Example 1 was carried out except that no anti-aging agent was added, and the rolling resistance characteristics, steering stability, and wet grip properties were evaluated.
The density of the entire blended oil used at this time was 1.02 g / cm ³ .

[Comparative Example 1]
In Example 1, except that 130 parts by mass of “Sample α3” produced in Production Example 1-3 was used instead of “Sample α1” produced in Production Example 1-1 as the modified conjugated diene polymer. The same operation as in Example 1 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample α3 contains 30 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 2]
In Example 2, except that 110 parts by mass of “Sample β2” produced in Production Example 2-2 was used instead of “Sample β1” produced in Production Example 2-1, as the modified conjugated diene polymer. The same operation as in Example 2 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample β2 contains 10 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 3]
In Example 3, except that 130 parts by mass of “Sample γ2” produced in Production Example 2-2 was used instead of “Sample γ1” produced in Production Example 3-1, as the modified conjugated diene polymer. The same operation as in Example 3 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Note that the sample γ2 contains 30 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 4]
In Example 7, the modified conjugated diene polymer was used except that 130 parts by mass of “Sample θ4” manufactured in Preparation Example 4-4 was used instead of “Sample θ2” manufactured in Preparation Example 4-2. The same operation as in Example 3 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample θ4 contains 30 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 5]
In Example 5, except that 107 parts by mass of “Sample α4” produced in Production Example 1-4 was used instead of “Sample α2” produced in Production Example 1-2 as the modified conjugated diene polymer. The same operation as that of No. 5 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample α4 contains 7 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 6]
In Comparative Example 1, 40 parts by mass of extender oil 1 is blended so that the blended oil amount is 70 parts by mass including the extender oil in sample α3, and 200 parts by mass of silica and silane coupling agent are blended. Was changed to 16 parts by mass, and the same operation as in Comparative Example 1 was carried out except that no carbon black was added, and the rolling resistance characteristics, the steering stability, and the wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 7]
In Example 8, as the modified conjugated diene polymer, Example 107 was used except that 107 parts by mass of “Sample θ5” produced in Production Example 4-5 was used instead of “Sample θ3” produced in Production Example 4-3. The same operation as in No. 8 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample θ5 contains 7 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 8]
In Comparative Example 4, 40 parts by mass of extender oil 1 is blended so that the blended oil amount is 70 parts by mass including the extender oil in sample θ4, and 200 parts by mass of silica and the silane coupling agent are blended. Was changed to 16 parts by mass, and the same operation as in Comparative Example 4 was performed except that no carbon black was added, and the rolling resistance characteristics, the steering stability, and the wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 9]
In Example 10, except that 130 parts by mass of “Sample ε2” produced in Production Example 5-2 was used instead of “Sample ε1” produced in Production Example 5-1, as the modified conjugated diene polymer. The same operation as in Example 10 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Note that the sample ε2 contains 30 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 10]
In Example 11, except that 130 parts by mass of “Sample σ2” produced in Production Example 6-2 was used instead of “Sample σ1” produced in Production Example 6-1 as the modified conjugated diene-based polymer. The same operation as in Example 11 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. The sample σ2 contains 30 parts by mass of the extending oil 1.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 11]
In Example 5, the modified conjugated diene-based polymer was carried out except that 7 parts by mass of “Sample α6” produced in Production Example 1-6 was used instead of “Sample α2” produced in Production Example 1-2. The same operation as in Example 5 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Sample α6 contains 7 parts by mass of modified silicone oil (Phenyl group-modified dimethyl silicone oil, SH510, manufactured by Toray Dow Corning Co., Ltd.).
The density of the entire blended oil used at this time was 0.99 g / cm ³ .

[Comparative Example 12]
In Example 1, except that 30 parts by mass of “Sample α5” produced in Production Example 1-5 was used instead of “Sample α1” produced in Production Example 1-1 as the modified conjugated diene polymer. The same operation as in Example 1 was performed, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated. Sample α5 contains 30 parts by mass of extender oil 2 (manufactured by Nanas, Nytex 4700, density 0.94 g / cm ³ ).
The density of the entire blended oil used at this time was 0.94 g / cm ³ .

[Comparative Example 13]
In Example 13, instead of using the high-density oil 1, the same operation as in Example 13 was carried out except that 40 parts by weight of the extending oil 1 was blended, and the rolling resistance characteristics, steering stability, and wet grip properties were evaluated. did.

[Comparative Example 14]
In Example 14, the same operation as in Example 14 was performed except that 30 parts by mass of the extending oil 1 was blended in place of the high-density oil 1, and the rolling resistance characteristics, steering stability, and wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 15]
In Example 15, the same operation as Example 15 was carried out except that 25.7 parts by mass of extension oil 1 was blended so that the amount of blended oil was 30 parts by mass including the part of extender oil 1 in sample θ6. The rolling resistance characteristics, steering stability, and wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 16]
In Example 16, the same operation as in Example 16 was performed except that 7 parts by mass of the extending oil 1 was blended in place of the high-density oil 2, and rolling resistance characteristics, steering stability, and wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

[Comparative Example 17]
In Example 17, the same operation as in Example 17 was performed except that 70 parts by mass of the extending oil 1 was blended in place of the high-density oil 1, and the rolling resistance characteristics, the steering stability, and the wet grip properties were evaluated.
The density of the whole blended oil used at this time was 0.95 g / cm ³ .

  The composition of Examples 1-17 and Comparative Examples 1-17 are shown in Table 3 and Table 4, and the evaluation results of these rolling resistance characteristics, steering stability and wet grip properties are shown in Table 5 to Table 20.

The symbols in Table 3 and Table 4 are shown below.
* 6 Vivamax 5000 (density 1.02 g / cm ³ )
* 7 Vivatec 500 (density 0.95 g / cm ³ )
* 8 Vivamax 5100 (density 1.01 g / cm ³ )
* 9 Density of the whole oil (high density oil + extension oil + modified silicone oil)
* 10 SH510 (density 0.99 g / cm ³ )
* 11 Nytex 4700 (density 0.94 g / cm ³ )
* 12 DCPD (hydrogenated cyclopentadiene)
* 13 T160 (modified terpene phenol resin)

From Table 5 to Table 20, it was found that the rubber composition of the present invention is highly excellent in the balance of rolling resistance characteristics, steering stability, and wet grip properties.
On the other hand, as in Comparative Examples 1 to 17, a material having a density less than 1.0 g / cm ³ as in the case of a conventional extending oil is inferior in the balance of rolling resistance characteristics, steering stability, and wet grip properties. I understood that.

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

Claims (7)

The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5, and contains a modified conjugated diene polymer (A) having adsorptivity to a silica column. Rubber component to
Oil (b),
A modified conjugated diene polymer composition comprising a conjugated diene polymer having a density exceeding 1.0 g / cm ³ . The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) is less than 1.5, and contains a modified conjugated diene polymer (A) having adsorptivity to a silica column. Rubber component to
A silica-based inorganic filler;
Oil (b),
Modified conjugated diene polymer composition, wherein the oil (b) has a density of 1.0 g / cm ³ or more.   The modified conjugated diene polymer composition according to claim 1 or 2, wherein the modified conjugated diene polymer (A) has a modification rate of 60% by mass or more.   The modified conjugated diene polymer composition according to claim 1 or 3, further comprising a silica-based inorganic filler.   The modified conjugated diene polymer composition according to any one of claims 1 to 4, further comprising carbon black.   The modified conjugated diene polymer composition according to any one of claims 1 to 5, which is used for a base tread.   A tire comprising a base tread containing a crosslinked product of the modified conjugated diene polymer composition according to any one of claims 1 to 6.