JP5615585B2 - Modified conjugated diene polymer, production method thereof, modified conjugated diene polymer composition, and tire - Google Patents

Description

  The present invention relates to a modified conjugated diene polymer, a production method thereof, a modified conjugated diene polymer composition, and a tire including the composition.

In recent years, environmental considerations, such as the suppression of carbon dioxide emissions, have become social demands, and the demand for lower fuel consumption for automobiles has increased. Under such circumstances, development of a material having low rolling resistance is demanded as a material for automobile tires, particularly tire treads that are in contact with the ground.
Conventionally, carbon black, silica, and the like have been used as reinforcing fillers for tire treads. When silica is used as the reinforcing filler, there is an advantage that low hysteresis loss and wet skid resistance can be improved.
On the other hand, since silica with a hydrophilic surface has a low affinity with a conjugated diene rubber and has a disadvantage of poor dispersibility compared with carbon black, with respect to carbon black with a hydrophobic surface, In order to improve dispersibility or to provide a bond between silica and rubber, it is necessary to contain a silane coupling agent separately.
In view of such problems related to silica, the dispersibility of silica in a conjugated diene rubber material can be improved by introducing functional groups having affinity and reactivity with silica at the end of rubber molecules having high mobility. Attempts have been made to reduce the hysteresis loss by improving and further sealing the rubber molecule end with a bond with silica particles.

For example, a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer end (for example, see Patent Document 1) or a modification obtained by reacting a glycidoxyalkoxysilane with a polymer end. Diene rubbers (for example, see Patent Document 2), modified diene rubbers obtained by reacting alkoxysilanes containing amino groups at the polymer ends (for example, see Patent Documents 3 and 4), and There have been proposals for compositions of these with silica.
In addition, the diene rubber is polymerized using a polyfunctional anionic polymerization initiator, and then modified with a modifying agent such as a glycidylamino group to increase the number of functionalized polymer ends, thereby diene rubber. A technique for improving the performance of a composition composed of silica and silica, that is, silica dispersibility and reducing hysteresis loss (see, for example, Patent Document 5) has also been proposed.

International Publication No. 01/23467 Pamphlet Japanese Patent Application Laid-Open No. 07-233217 JP 2001-158834 A JP 2003-171418 A JP 2006-306962 A

However, in recent years, with the further increase in demand for fuel efficiency, development of a rubber composition having further reduced hysteresis loss has been demanded.
The problem of the present invention is that when a vulcanized product containing a silica-based inorganic filler is used, it has an excellent balance between low hysteresis loss and safety-related characteristics such as wet skid resistance and low temperature characteristics, and has practically sufficient resistance. To provide a modified conjugated diene polymer having wearability and fracture strength and satisfying good processability, a production method thereof, a modified conjugated diene polymer composition, and a tire including the composition. Objective.

As a result of intensive studies to solve the problems of the prior art, the present inventors have polymerized using a specific polyfunctional anionic polymerization initiator, and a compound having a specific functional group at a polymerization active terminal. The present inventors have found that the above problems can be solved by using a modified conjugated diene polymer obtained by modification, and have completed the present invention.
The present invention is as follows.
[1]
Using a polyfunctional anionic polymerization initiator prepared with a molar ratio of polyvinyl aromatic compound and organolithium compound (polyvinyl aromatic compound / organolithium compound) in the range of 0.05 to 1.0,
The following formula (1), formula (2), and formula (3) are attached to the polymerization active terminal of a conjugated diene polymer obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound. Or the modified conjugated diene polymer obtained by making the compound represented by Formula (4), or these condensates react.

(In the formula (1), A ¹ is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, imine, and sulfide, and R ¹ is a single bond or having 1 to 1 carbon atoms. 20 is a divalent hydrocarbon group, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, d is an integer of 1 to 3, and a plurality of R ³ Os are present. some cases, each R ^{3 O} or different and be identical to one another, when R ² are a plurality, each R ² may being the same or different.)

(In the formula (2), R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or two of them are bonded together to form a silicon atom to which they are bonded. Ring may be formed, e is an integer of 1 to 2, and f is an integer of 1 to 10.)

(In Formula (3), the definition of R < ⁴ > -R < ⁹ > is the same as Formula (2), and g is an integer of 1-2.)

(In the formula (4), ^{X 1} and ^{X 2} are alkoxy groups of halogen atom or a C ^{1-20, R 10} and ^{R 11} are each a monovalent hydrocarbon group having 1 to 20 carbon atoms Each of A ² and A ³ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ⁴ is a group represented by the following formulas (5), (6), or (7). When a plurality of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ² , A ³ or A ⁴ are present, they may be the same or different from each other, p and q Are each an integer of 0 to 3. h is an integer of 0 to 20, and when h is 2 or more, the plurality of repeating units represented by (A ² -A ⁴ -A ³ ) are different. In the compound represented by formula (4), the number of halogen atoms and the number of carbon atoms of 1 to The total number of 20 alkoxy groups is 5 or more.)

(In the formula (5), ^{X 3} is ^{.R 12} is an alkoxy group having a halogen atom or a C1-20 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plurality of ^{X 3} or ^{R 12} is When present, they may be the same or different, r is an integer of 0 to 2, i is an integer of 0 to 20. When i is 2 or more, (SiX ³ _The plurality of repeating units represented by _r R ¹² _2-r ) may be different from each other, and when A ⁴ is represented by the formula (5), [p + (h × i × r) + Q] is an integer of 5 or more.)

(In Formula (6), R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When A ⁴ is represented by Formula (6), (p + q) is 5 or 6 .)

(In the formula (7), ^{A 5} is a divalent hydrocarbon group of a single bond or a C 1-20, ^{X 5} is ^{.R 14} is a carbon number of an alkoxy group a halogen atom, or 1 to 20 carbon atoms It is a monovalent hydrocarbon group of 1 to 20. When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different, and s is an integer of 0 to 3. . in the case ^{where a 4} is represented by the formula (7), which is [p + (h × s) + q] is an integer of 5 or more.)

[2]
The modified conjugated diene polymer according to [1], wherein the molar ratio of the polyvinyl aromatic compound and lithium is in the range of 0.1 to 0.45.
[3]
The modified conjugated diene according to [1] or [2], wherein the peak area on the lowest molecular weight side is 20 to 50% of the entire chromatogram area in gel permeation chromatography measurement using a polystyrene gel packed column. Polymer.
[4]
The molar ratio of the polyvinyl aromatic compound and the organolithium compound (polyvinyl aromatic compound / organolithium compound) is reacted in the range of 0.05 to 1.0,
Preparing a polyfunctional anionic polymerization initiator;
Using the polyfunctional anionic polymerization initiator, polymerizing a conjugated diene compound, or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
A step of reacting a compound represented by the following formula (1), formula (2), formula (3) or formula (4), or a condensate thereof with the polymerization active terminal of the conjugated diene polymer;
A process for producing a modified conjugated diene-based polymer.

(In the formula (1), A ¹ is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, imine, and sulfide, and R ¹ is a single bond or having 1 to 1 carbon atoms. 20 is a divalent hydrocarbon group, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, d is an integer of 1 to 3, and a plurality of R ³ Os are present. some cases, each R ^{3 O} or different and be identical to one another, when R ² are a plurality, each R ² may being the same or different.)

(In the formula (2), R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or two of them are bonded together to form a silicon atom to which they are bonded. Ring may be formed, e is an integer of 1 to 2, and f is an integer of 1 to 10.)

(In Formula (3), the definition of R < ⁴ > -R < ⁹ > is the same as Formula (2), and g is an integer of 1-2.)

(In the formula (4), ^{X 1} and ^{X 2} are alkoxy groups of halogen atom or a C ^{1-20, R 10} and ^{R 11} are each a monovalent hydrocarbon group having 1 to 20 carbon atoms Each of A ² and A ³ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ⁴ is a group represented by the following formulas (5), (6), or (7). When a plurality of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ² , A ³ or A ⁴ are present, they may be the same or different from each other, p and q Are each an integer of 0 to 3. h is an integer of 0 to 20, and when h is 2 or more, the plurality of repeating units represented by (A ² -A ⁴ -A ³ ) are different. In the compound represented by formula (4), the number of halogen atoms and the number of carbon atoms of 1 to The total number of 20 alkoxy groups is 5 or more.)

(In the formula (5), ^{X 3} is ^{.R 12} is an alkoxy group having a halogen atom or a C1-20 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plurality of ^{X 3} or ^{R 12} is When present, they may be the same or different, r is an integer of 0 to 2, i is an integer of 0 to 20. When i is 2 or more, (SiX ³ _The plurality of repeating units represented by _r R ¹² _2-r ) may be different from each other, and when A ⁴ is represented by the formula (5), [p + (h × i × r) + Q] is an integer of 5 or more.)

(In Formula (6), R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When A ⁴ is represented by Formula (6), (p + q) is 5 or 6 .)

(In the formula (7), ^{A 5} is a divalent hydrocarbon group of a single bond or a C 1-20, ^{X 5} is ^{.R 14} is a carbon number of an alkoxy group a halogen atom, or 1 to 20 carbon atoms It is a monovalent hydrocarbon group of 1 to 20. When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different, and s is an integer of 0 to 3. . in the case ^{where a 4} is represented by the formula (7), which is [p + (h × s) + q] is an integer of 5 or more.)

[5]
The method for producing a modified conjugated diene polymer according to [4] above, wherein the molar ratio of the polyvinyl aromatic compound to the organolithium compound is in the range of 0.1 to 0.45.
[6]
0.5 to 300 parts by mass of silica-based inorganic filler is added to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer according to any one of [1] to [3]. A modified conjugated diene polymer composition.
[7]
The modified conjugated diene polymer composition according to [6] above, further containing 0.5 to 100 parts by mass of carbon black with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer. object.
[8]
The modified conjugated diene polymer composition according to [6] or [7], wherein the silica-based inorganic filler has a nitrogen adsorption specific surface area of 170 m ² / g or more.
[9]
A tire comprising the modified conjugated diene polymer composition according to any one of [6] to [8].

  According to the present invention, when a vulcanizate containing a silica-based inorganic filler is used, it has an excellent balance between low hysteresis loss and safety-related characteristics such as wet skid resistance and low temperature characteristics, and has practically sufficient resistance. Provided are a modified conjugated diene polymer, a production method thereof, a modified conjugated diene polymer composition, and a tire, which have wearability and fracture strength, and satisfy satisfactory processability.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.
In the following, the modified conjugated diene polymer of this embodiment will be described together with its production method.
[Modified Conjugated Diene Polymer]
The modified conjugated diene polymer of the present embodiment is a polyfunctional compound prepared with a molar ratio of polyvinyl aromatic compound and organolithium compound (polyvinyl aromatic compound / organolithium compound) in the range of 0.05 to 1.0. An anionic polymerization initiator is used to polymerize a conjugated diene compound, or to copolymerize a conjugated diene compound and an aromatic vinyl compound, and to the polymerization active terminal of a conjugated diene polymer obtained by the formula (1), formula (2) ), A compound represented by formula (3) or formula (4), or a modified conjugated diene polymer obtained by reacting these condensates.

[Method for producing modified conjugated diene polymer]
In the production method of the modified conjugated diene polymer of the present embodiment, a polyvinyl aromatic compound and an organic lithium compound are reacted, and the molar ratio of polyvinyl aromatic compound / organic lithium compound is in the range of 0.05 to 1.0. A step of preparing a polyfunctional anionic polymerization initiator of
Using the polyfunctional anionic polymerization initiator, polymerizing a conjugated diene compound, or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
A step of reacting a compound represented by the formula (1), the formula (2), the formula (3) or the formula (4), or a condensate thereof with the polymerization active terminal of the conjugated diene polymer;
Have
The modified conjugated diene polymer of the present embodiment will be described below together with the production steps with respect to the materials used and the conditions for producing them.

(Polyfunctional anionic polymerization initiator)
First, the compound represented by the formula (1), the formula (2), the formula (3) or the formula (4) (modifier), or a condensate thereof is attached to the polymerization active terminal of the conjugated diene polymer described above. The polyfunctional anionic polymerization initiator used in the step of polymerizing the conjugated diene polymer before the modification will be described.
A polyfunctional anionic polymerization initiator can be prepared by reacting a polyvinyl aromatic compound and an organic lithium 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 polyvinyl aroma. A polyfunctional anion initiator prepared by a method of reacting a monoorganolithium compound in the presence of a group compound is preferred.
In addition, in order to promote and stabilize the formation of the polyfunctional anionic polymerization initiator, it is preferable to add a Lewis base into the system during the preparation.

<Polyvinyl aromatic compound>
Examples of the polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator 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. These may be used alone or in combination of two or more.
In particular, divinyl benzene and diisopropenyl benzene are preferable, and a mixture of these o-, m-, and p-isomers may be used. For industrial use, it is economically advantageous to use a mixture of these isomers.

<Conjugated diene compounds and monovinyl aromatic compounds>
For the preparation of the polyfunctional anionic polymerization initiator, a conjugated diene compound and / or a monoaromatic vinyl compound can be used together with the above-described polyvinyl aromatic compound.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, Examples include 1,3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable.
Examples of the monovinyl aromatic compound include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and styrene is particularly preferable.
The conjugated diene compound and / or the monoaromatic vinyl compound has a polystyrene-reduced weight average molecular weight of 500 to 20,000 in the polyfunctional anionic polymerization initiator measured by GPC (gel permeation chromatography). It is preferable to add to 1,000, and it is still more preferable to add so that it may become 1,000-10,000.

<Organic lithium compounds>
Examples of the organolithium compound used for the preparation of the polyfunctional anionic polymerization initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium. Compound; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4- Dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4 Polyfunctional organolithium compounds such as 6-triethylbenzene can be mentioned.
In particular, a monoorganolithium compound of n-butyllithium, sec-butyllithium, or tert-butyllithium is preferable.

<Hydrocarbon solvent>
Examples of the hydrocarbon solvent used for the preparation of the polyfunctional anionic polymerization initiator include aliphatic hydrocarbons such as butane, pentane, hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, toluene, xylene and the like. And aromatic hydrocarbons.

<Lewis base>
In the preparation of the polyfunctional anionic polymerization initiator, the formation can be promoted and stabilized by adding a Lewis base into the system.
Examples of the Lewis base include tertiary monoamine, tertiary diamine, chain or cyclic ether.
Examples of the tertiary monoamine include trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, N-dimethylformamide diisopropyl acetal, N, N -Compounds such as dimethylformamide dicyclohexyl acetal.

As the tertiary diamine, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane Diamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N′-tetramethylhexanediamine, dipiperidi And compounds such as nopentane and dipiperidinoethane.
Examples of the chain ether include 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 tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, and 2,2-bis (2-oxolanyl). ) Butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, and the like.

Among the Lewis bases, tertiary monoamine trimethylamine, triethylamine, tertiary diamine N, N, N ′, N′-tetramethylethylenediamine, and cyclic ether tetrahydrofuran, 2,2-bis (2-oxolanyl). ) Propane is preferred.
The said Lewis base may be used independently and may be used in combination of 2 or more type.
The amount of the polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator is in the range of 0.05 to 1.0 mol with respect to 1 mol of the organic lithium compound.
As a result, a polyfunctional anionic polymerization initiator having a molar ratio of polyvinyl aromatic compound / organolithium compound in the range of 0.05 to 1.0 is obtained.

  The greater the amount of the polyvinyl aromatic compound used relative to the organolithium compound, the greater the proportion of molecular chain terminals to which functional groups are imparted by the modification reaction of the conjugated diene polymer described later, and the silica particles described later. Affinity and reactivity are improved, the balance between low hysteresis loss and wet skid resistance in the modified conjugated diene polymer composition is improved, and wear resistance and fracture characteristics are also improved. On the other hand, the smaller the amount of the polyvinyl aromatic compound used relative to the organolithium compound, the better the workability at the time of kneading the composition. The process Mooney viscosity can be used as an index for processability. When the compound Mooney viscosity is too high, adverse effects such as an increase in torque during kneading and an increase in power consumption occur. In addition, it may be difficult to produce a uniform sheet in the sheeting process after kneading. In general, when the low hysteresis loss is improved, the Mooney viscosity of the compound tends to increase and the processability tends to deteriorate, but it is practically important not to make it too high. From these balances, the amount of the polyvinyl aromatic compound is preferably in the range of 0.1 to 0.5 mol, more preferably in the range of 0.1 to 0.45, with respect to 1 mol of the organic lithium compound, A range of 0.4 is more preferred.

Moreover, when preparing a polyfunctional anionic polymerization initiator, when adding a Lewis base, it adds within the range of 30-50,000 ppm with respect to the said solvent used when preparing a polyfunctional anionic polymerization initiator. It is preferable to add in the range of 200 to 20,000 ppm.
Addition of 30 ppm or more is preferable in order to fully express the effect of promoting and stabilizing the reaction, ensuring the degree of freedom of microstructure adjustment in the subsequent polymerization step, and recovering and purifying the solvent after polymerization In consideration of separation from the polymerization solvent in, it is preferably added at 50,000 ppm or less.

The temperature for preparing the polyfunctional anionic polymerization initiator is preferably in the range of 10 ° C to 140 ° C, and more preferably in the range of 35 ° C to 110 ° C.
From the viewpoint of productivity, it is preferably 10 ° C or higher, and preferably 140 ° C or lower in order to suppress side reactions due to high temperatures.
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.

(Conjugated diene polymer)
The conjugated diene polymer, which is a state before modification of the modified conjugated diene polymer of the present embodiment, is obtained by polymerizing a conjugated diene compound using the polyfunctional anionic polymerization initiator described above, or a conjugated diene compound and an aromatic. It is obtained by copolymerizing with a vinyl compound.
In the polymerization step of the conjugated diene polymer, the polyfunctional anionic polymerization initiator described above is prepared in a predetermined reactor in advance, and the polymerization of the conjugated diene compound or the 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 for performing polymerization, or a polyfunctional anionic polymerization initiator is prepared in a reactor for performing polymerization or copolymerization described later, These monomers may be supplied to carry out the polymerization reaction.
From the viewpoint of productivity and quality stability at the time of mass production of a polymer, a polyfunctional anionic polymerization initiator is prepared in advance in a predetermined reactor, and this is used as a reactor for polymerization as required. It is preferable to carry out the polymerization of the conjugated diene compound or the copolymerization of the conjugated diene compound and the aromatic vinyl compound.
The polymerization of the conjugated diene polymer can be carried out by a polymerization method such as a batch method or a continuous method in one reactor or two or more connected reactors. In the modification reaction described later, it is preferable to carry out the polymerization in a batch reactor from the viewpoint of obtaining a polymer having a higher modification rate.

<Polar compound>
For the production of conjugated diene polymers, the purpose is to randomly copolymerize aromatic vinyl compounds with conjugated diene compounds, as a vinylating agent to control the microstructure of the conjugated diene part, and to further improve the polymerization rate. For this purpose, a small amount of the following polar compound may be added.

Examples of the polar compound include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; alkali metal alkoxides such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, sodium amylate Compound: Examples include phosphine compounds such as triphenylphosphine.
These polar compounds may be used alone or in combination of two or more.

Although the usage-amount of a polar compound is selected according to the objective and the grade of an effect, it is 0.01-100 mol normally with respect to 1 mol of lithium in a polyfunctional anionic polymerization initiator.
Such a polar compound (vinylating agent) can be used in an appropriate amount depending on the desired vinyl bond amount as a microstructure modifier for the polymer diene moiety.
Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can adjust the distribution of the aromatic vinyl compound and the amount of styrene block.
As a randomizing method, a method of intermittently adding a part of 1.3-butadiene during the copolymerization can be used as described in JP-A No. 59-140221.

<Conjugated diene compound>
Examples of the conjugated diene compound used for the synthesis of the conjugated diene polymer include 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 the like. Among these, 1,3-butadiene and isoprene are particularly preferable, and these may be used alone or in combination of two or more.
When allenes and acetylenes are contained as impurities, the modification reaction described later is inhibited. Therefore, the total of these concentrations is preferably 200 ppm or less, more preferably 100 ppm or less, and 50 ppm or less. More preferably.

<Aromatic vinyl compound>
Examples of the aromatic vinyl compound used for the synthesis of the conjugated diene polymer include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is particularly preferable, and these may be used alone or in combination of two or more.
<Polymerization solvent>
The conjugated diene polymer is polymerized in a predetermined solvent.
As the solvent, for example, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons are used. 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; There may be mentioned hydrocarbons composed of mixtures thereof.

<Polymerization conditions>
The polymerization temperature of the conjugated diene polymer is not particularly limited as long as the living anion polymerization proceeds, but is preferably 0 ° C. or higher from the viewpoint of productivity, and the amount of modification reaction to the active terminal after the polymerization is completed. It is preferable to carry out at 120 degrees C or less from a viewpoint of ensuring sufficient. More preferably, it is the range of 20-100 degreeC, More preferably, it is the range of 30-85 degreeC.
The polymerization temperature can be controlled by taking into consideration that the polymerization is an exothermic reaction, further adjusting the monomer and solvent feed temperatures, controlling the monomer concentration, and cooling and heating from the outside of the reactor.
The conjugated diene compound, aromatic vinyl compound, and polymerization solvent described above are each used alone or before a mixture of these is subjected to a polymerization reaction in advance, using impurities such as allenes and acetylenes as organometallic compounds. Can also be processed. Thereby, the active terminal amount of the polymer before the modification reaction becomes a high concentration, and a higher modification rate can be achieved.

<Structure of Conjugated Diene Polymer>
In the modified conjugated diene polymer composition containing a modified conjugated diene polymer and a filler, which will be described later, when wet skid characteristics are important, the content of aromatic vinyl units in the conjugated diene polymer is 1-50 mass% is preferable, 10-45 mass% is more preferable, and 20-40 mass% is further more preferable.
From the viewpoint of obtaining excellent wet skid resistance, the content of the aromatic vinyl unit in the conjugated diene copolymer before modification is preferably 1% by mass or more, from the viewpoint of low hysteresis loss and wear resistance. Is preferably 50% by mass or less.
Further, the proportion of 1,2- or 3,4-bond in the conjugated diene bond unit of the conjugated diene polymer before modification is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, 25-65 mass% is further more preferable.

From the viewpoint of obtaining excellent wet skid resistance, the proportion of 1,2- or 3,4-bond in the conjugated diene bond unit of the conjugated diene polymer is 10% by mass or more as described above. Preferably, it is preferably 80% by mass or less from the viewpoints of low hysteresis loss and wear resistance.
The composition distribution of the conjugated diene and the aromatic vinyl in the conjugated diene-aromatic vinyl copolymer chain may be uniform in the molecular chain or non-uniformly distributed in the molecular chain. It may be present as a block.

On the other hand, in the modified conjugated diene polymer composition containing a modified conjugated diene polymer and a filler, which will be described later, when the purpose is to obtain excellent low temperature characteristics, the conjugated diene-aromatic vinyl is used. The content of the aromatic vinyl unit in the copolymer is preferably 10% by mass or less, and more preferably a conjugated diene homopolymer. The proportion of 1,2- or 3,4-bonds in the conjugated diene bond unit of the conjugated diene polymer before modification is preferably 30% by mass or less, and 25% by mass or less. Is more preferable.
When each component ratio is in the above range, a composition having a low glass transition temperature and excellent low-temperature characteristics can be obtained.

(Modifier)
In the modified conjugated diene polymer of this embodiment, the polymerization active terminal is modified with a modifier.
Specifically, the above-described polyfunctional anionic polymerization initiator is used to polymerize the conjugated diene compound described above or copolymerize the conjugated diene compound and the aromatic vinyl compound to produce a conjugated diene-based polymer. The modified conjugated diene polymer of this embodiment can be obtained by reacting a specific compound with the polymerization active terminal of the diene polymer.
As a specific compound used for the modification reaction, a compound represented by the following formula (1), formula (2), formula (3) or formula (4), or a condensate of formula (1), formula (2) A condensate, a condensate of formula (3) or a condensate of formula (4) may be mentioned.
Here, the condensate represents a compound in which a part of the alkoxysilyl group (—SiOR) in the compound is converted to siloxane (—Si—O—Si—) by condensation.
These compounds do not have active hydrogen. Active hydrogen means a hydrogen atom bonded to O, N or the like having a high electronegativity (Tokyo Kagaku Doujin "Chemical Dictionary").

(In the formula (1), A ¹ is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, imine, and sulfide, and R ¹ is a single bond or having 1 to 1 carbon atoms. 20 is a divalent hydrocarbon group, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, d is an integer of 1 to 3, and a plurality of R ³ Os are present. some cases, each R ^{3 O} or different and be identical to one another, when R ² are a plurality, each R ² may being the same or different.)

(In the formula (2), R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or two of them are bonded together to form a silicon atom to which they are bonded. Ring may be formed, e is an integer of 1 to 2, and f is an integer of 1 to 10.)

(In Formula (3), the definition of R < ⁴ > -R < ⁹ > is the same as Formula (2), and g is an integer of 1-2.)

(In the formula (4), ^{X 1} and ^{X 2} are alkoxy groups of halogen atom or a C ^{1-20, R 10} and ^{R 11} are each a monovalent hydrocarbon group having 1 to 20 carbon atoms Each of A ² and A ³ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ⁴ is a group represented by the following formulas (5), (6), or (7). When a plurality of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ² , A ³ or A ⁴ are present, they may be the same or different from each other, p and q Are each an integer of 0 to 3. h is an integer of 0 to 20, and when h is 2 or more, the plurality of repeating units represented by (A ² -A ⁴ -A ³ ) are different. In the compound represented by formula (4), the number of halogen atoms and the number of carbon atoms of 1 to The total number of 20 alkoxy groups is 5 or more.)

(In the formula (5), ^{X 3} is ^{.R 12} is an alkoxy group having a halogen atom or a C1-20 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plurality of ^{X 3} or ^{R 12} is When present, they may be the same or different, r is an integer of 0 to 2, i is an integer of 0 to 20. When i is 2 or more, (SiX ³ _The plurality of repeating units represented by _r R ¹² _2-r ) may be different from each other, and when A ⁴ is represented by the formula (5), [p + (h × i × r) + Q] is an integer of 5 or more.)

(In Formula (6), R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When A ⁴ is represented by Formula (6), (p + q) is 5 or 6 .)

(In the formula (7), ^{A 5} is a divalent hydrocarbon group of a single bond or a C 1-20, ^{X 5} is ^{.R 14} is a carbon number of an alkoxy group a halogen atom, or 1 to 20 carbon atoms It is a monovalent hydrocarbon group of 1 to 20. When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different, and s is an integer of 0 to 3. . in the case ^{where a 4} is represented by the formula (7), which is [p + (h × s) + q] is an integer of 5 or more.)

Here, Formula (1), Formula (2), Formula (3), and Formula (4) will be specifically described.
First, equation (1) will be described.
A ¹ is a monovalent group having at least one functional group selected from a tertiary amine, pyridine, cyan, imine, and sulfide, and the tertiary amine includes a cyclic tertiary amine and an acyclic tertiary amine. Further, the cyclic tertiary amine contains an ether bond and a thioether bond as a part of the ring, and the acyclic tertiary amine contains an N, N-disubstituted aromatic such as N, N-disubstituted aniline.
R ¹ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. When R ¹ is a single bond, it can be represented by the following formula (8) in which silicon and A ¹ are directly bonded.

(In the formula ^{(8), A 1, R} 2, R 3, d definition is the same as equation (1).)

When R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms And 20 aralkylene groups. Among these, an alkylene group having 1 to 20 carbon atoms is preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.
The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ² and R ³ includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a carbon number. Examples thereof include 7 to 18 aralkyl groups.

The alkyl group and alkenyl group may be linear, branched or cyclic. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl Group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group and the like.
The aryl group may have a substituent such as a lower alkyl group on the aromatic ring. For example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.
The aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring. For example, benzyl group, phenethyl group, naphthylmethyl group and the like can be mentioned.
d is an integer of 1 to 3, and preferably 2 or 3. If R 3 ^O is plural, each R ^{3 O} or different and be identical to one another, when R ² are a plurality, each R ² may being the same or different.

Specific examples of the compound represented by the formula (1) are shown below.
For example, when A ¹ contains a cyclic tertiary amine, [3- (1-hexamethyleneimino) propyl] triethoxysilane, [(1-hexamethyleneimino) methyl] triethoxysilane, [2- (1- Hexamethyleneimino) ethyl] triethoxysilane, [3- (1-pyrrolidinyl) propyl] triethoxysilane, [3- (1-heptamethyleneimino) propyl] triethoxysilane, [3- (1-dodecamethyleneimino) Propyl] triethoxysilane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 3- [10- (triethoxysilyl) decyl] -4-oxazoline and their triethoxysilyl compounds Corresponding trimethoxysilyl compound, methyldiethoxysilyl compound, ethyldiethoxysilyl compound, methyldi Tokishishiriru compound, ethyl dimethoxy silyl compounds, and the like.

For example, when A ¹ contains an acyclic tertiary amine, [3- (dimethylamino) propyl]] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [2- (dimethylamino) ethyl] tri Ethoxysilane, [3- (dibutylamino) propyl] triethoxysilane, [(3-methyl-3-ethylamino) propyl] triethoxysilane and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxy Examples thereof include a silyl compound, an ethyldiethoxysilyl compound, a methyldimethoxysilyl compound, and an ethyldimethoxysilyl compound.

For example, when A ¹ contains pyridine, 2- (triethoxysilylethyl) pyridine and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds corresponding to these triethoxysilyl compounds And ethyldimethoxysilyl compounds.
For example, when A ¹ contains cyan, 2-cyanoethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 11-cyanoundecyltriethoxysilane, and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, Examples thereof include ethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds and the like. Of these, 3-cyanopropyltriethoxysilane is preferred.

For example, when A ¹ contains imine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) ) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- ( 4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their triethoxysilyl Trimethoxysilyl compound, methyldiethoxysilyl compound, ethyldiethoxysilyl compound, methyldimethoxysilyl compound corresponding to the compound Products, ethyldimethoxysilyl compounds and the like.

Next, Formula (2) and Formula (3) will be described.
Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms of R ⁴ include an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, and 7 to 12 carbon atoms. And an aralkylene group. Among these, an alkylene group having 1 to 12 carbon atoms is preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear. Examples of the linear alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, and a propylene group.

The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁵ and R ⁶ includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, and the number of carbon atoms. Examples thereof include an aralkyl group having 7 to 18 carbon atoms, and an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

When R ⁷ , R ⁸ and R ⁹ are a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl having 6 to 18 carbon atoms Group, an aralkyl group having 7 to 18 carbon atoms and the like, and an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.
When two of R ⁷ , R ⁸ and R ⁹ are bonded to form a ring together with the silicon atom to which they are bonded, the ring is preferably a 4-7 membered ring.
Furthermore, the —SiR ⁷ R ⁸ R ⁹ group is a protecting group for nitrogen to which silicon is bonded, and can be converted to a primary amino group by deprotection (hydrolysis) after the modification reaction. Examples of the protecting group include an alkylsilyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, and an ethylmethylphenylsilyl group.

Specific examples of the compound represented by the formula (2) are shown below.
N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldi Examples thereof include an ethoxysilyl compound, a methyldimethoxysilyl compound, and an ethyldimethoxysilyl compound.
Specific examples of the compound represented by formula (3) are shown below.
1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane and dimethoxysilyl compounds, methylethoxysilyl compounds, ethylethoxysilyl compounds, methylmethoxysilyl compounds, ethylmethoxy corresponding to these diethoxysilyl compounds A silyl compound etc. are mentioned.

Finally, Equation (4) will be described.
X ¹ and X ² are a halogen atom or an alkoxy group having 1 to 20 carbon atoms. When a plurality of X ¹ or X ² are present, they may be the same or different, but X ¹ and X ² are the same, that is, both are halogen atoms or both are alkoxy having 1 to 20 carbon atoms It is preferably a group.
Although it does not specifically limit as a halogen atom, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.
1-10 are preferable and, as for carbon number of an alkoxy group, 1-6 are more preferable.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexoxy group. Among these, a methoxy group and an ethoxy group are preferable from the viewpoint of ending the reaction time with the polymer having an active terminal in a short time.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁰ and R ¹¹ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. Examples thereof include aralkyl groups of 7 to 20.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a 2-phenylethyl group, and a 3-phenylethyl group.
Among these, it is preferable that it is a C1-C20 alkyl group, and it is more preferable that it is a C1-C10 alkyl group. Among these, a methyl group or an ethyl group is preferable. In addition, these alkyl groups, aralkyl groups, and aryl groups may have a substituent at an arbitrary position.

R ¹⁰ and R ¹¹ may be the same or different from each other. When a plurality of R ¹⁰ or R ¹¹ are present, they may be the same or different from each other.
A ² and A ³ are each a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. When a plurality of A ² or A ³ are present, they may be the same or different.
When A ² or A ³ is a single bond, the formula (4) can be expressed by the following formula (9), formula (10), or formula (11) in which silicon and A ⁴ are directly bonded.

(In Formula (9), Formula (10), and Formula (11), the definition of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ⁴ , h, p, q is the same as that in Formula (4). In Formula (9), A ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ² in Formula (10).

When A ² and A ³ are a C 1-20 divalent hydrocarbon group, a C 1-20 alkylene group, a C 2-20 alkylidene group, a C 3-6 cycloalkylene group, Examples include an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20 carbon atoms. Note that the alkylene group having 1 to 20 carbon atoms includes a linear alkylene group having 1 to 20 carbon atoms and a branched alkylene group having 3 to 20 carbon atoms.
As a C1-C20 linear alkylene group, a methylene group, ethylene group, n-propylene group etc. are mentioned, for example.

Examples of the branched alkylene group having 3 to 20 carbon atoms include an isopropylene group.
Examples of the alkylidene group having 2 to 20 carbon atoms include an ethylidene group, an isopropylidene group, and a vinylidene group.
Examples of the cycloalkylene group having 3 to 6 carbon atoms include a cyclohexylene group.
Examples of the arylene group having 6 to 20 carbon atoms include a phenylene group.
A ² and A ³ are preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.
In Formula (4), A ⁴ is a group represented by Formula (5), Formula (6), or Formula (7). When a plurality of A ⁴ are present, they may be the same or different.

Here, Formula (5), Formula (6), and Formula (7) will be specifically described.
First, equation (5) will be described.
X ³ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and specific examples thereof are the same as those exemplified for X ¹ and X ² .
R ¹² is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof are the same as those exemplified for R ¹⁰ and R ¹¹ .
When a plurality of X ³ or R ¹² are present, they may be the same or different.
r is an integer of 0 to 2, and i is an integer of 0 to 20. i is preferably an integer of 0 to 10, more preferably an integer of 1 to 3, and particularly preferably 1. When i is 2 or more, the plurality of repeating units represented by-(SiX ³ _r R ¹² _2-r )-may be different from each other. In the case ^{where A 4} is represented by the formula (5), [p + ( h × i × r) + q] is an integer of 5 or more.

Next, equation (6) will be described.
R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same ones as exemplified for R ¹⁰ and R ¹¹ . In the case ^{where A 4} is represented by the formula (6), (p + q ) is a 5 or 6.
Finally, Equation (7) will be described.
A ⁵ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include the same ones as exemplified for A ² and A ³ .
X ⁵ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and specific examples thereof are the same as those exemplified for X ¹ and X ² .
R ¹⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof are the same as those exemplified for R ¹⁰ and R ¹¹ .
When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different.
s is an integer of 0-3. In the case ^{where A 4} is represented by the formula (7), which is [p + (h × s) + q] is an integer of 5 or more.

In the formula (4), the case where X ¹ and X ² are both halogen atoms will be described.
In Formula (4), when X ¹ and X ² are both halogen atoms, A ⁴ is preferably a group represented by Formula (5). In this case, in the formula (5), X ³ is preferably a halogen atom. That is, in this case, the modifier represented by the formula (4) is a silicon halide compound.
The case where Formula (4) is a silicon halide compound will be described.
When Formula (4) is a silicon halide compound, it preferably has 5 to 10 halogen atoms in one molecule, particularly preferably 6 to 9 halogen atoms in one molecule. Most preferably, it has 6 halogen atoms.
The halogen atoms contained in the compound represented by the formula (4) may be the same or different, but from the viewpoint of facilitating the treatment of the salt by-produced by the modification reaction, all the halogen atoms are chlorine. Particularly preferred is an atom.

  As a silicon halide compound preferable as the modifier of the present invention, the following formula (12) may be mentioned.

In Formula (12), X ¹ and X ² are halogen atoms, and when a plurality of X ¹ or X ² are present, they may be different halogen atoms.
R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Among these, an alkyl group having 1 to 20 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
j is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6, and particularly preferably an integer of 0 to 2.
p is 2 or 3, and is more preferably 3.

Specific examples of the compound represented by formula (12) are shown below.
Hexachlorodisilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, 1,3-bis (trichlorosilyl) propane, 1,4-bis (trichlorosilyl) butane, 1,5-bis (trichloro) Silyl) pentane, 1,6-bis (trichlorosilyl) hexane and the like.
One of these silicon halide compounds may be used alone, or two or more thereof may be used in combination.

In the formula (4), the case where X ¹ and X ² are both an alkoxy group having 1 to 20 carbon atoms will be described.
In Formula (4), when X ¹ and X ² are both an alkoxy group having 1 to 20 carbon atoms, A ⁴ is a group represented by Formula (5), Formula (6), or Formula (7). It is preferable.
In this case, in Formula (5), X ³ is preferably an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkoxy group having 1 to 10 carbon atoms.
In Formula (7), X ⁵ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Particularly preferred.
In these cases, the modifier represented by the formula (4) is an alkoxysilane compound.

Specific examples of the group represented by the formula (6) include a methylimino group, an ethylimino group, a propylimino group, a phenylimino group, a benzylimino group, and the like.
Specific examples of the group represented by the formula (7) include a trimethoxysilylpropylimino group and a triethoxysilylpropylimino group.
The case where Formula (4) is an alkoxysilane compound will be described.
When Formula (4) is an alkoxysilane compound, it preferably has 5 or more alkoxy groups in one molecule, more preferably 5 to 10 alkoxy groups, and 6 to 9 alkoxy groups. More preferably, it preferably has 6 alkoxy groups.

  Examples of the alkoxysilane compound preferable as the modifier of the present invention include the following formula (13), formula (14), and formula (15).

In Formula (13), Formula (14), and Formula (15), X ¹ , X ² and X ⁵ are each an alkoxy group having 1 to 20 carbon atoms, and when there are a plurality of X ¹ , X ² or X ⁵ , Each may be the same or different.
R ¹⁰ and R ¹⁴ are each a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.
R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms.
A ^{6 to} A ¹¹ are a single bond, a polymethylene group having 1 to 20 carbon atoms (— (CH ₂ ) _k —), an arylene group, or a cycloalkylene group. In A ^{6 to} A ¹¹ , the number k of methylene groups may be the same or different. Moreover, it is preferable that k is an integer of 1-8.
In Formula (13) and Formula (14), p is 2 or 3, and in Formula (15), p and s are each an integer of 0 to 3, and (p + s) is an integer of 2 to 6. .

Specific examples of the compound represented by formula (13) are shown below.
Hexaethoxydisilane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) propane, bis (triethoxysilyl) butane, bis (triethoxysilyl) heptane, bis (triethoxysilyl) Examples include hexane, bis (triethoxysilyl) benzene, bis (triethoxysilyl) cyclohexane, bis (3-triethoxysilylpropyl) ethane, and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds.

Specific examples of the compound represented by formula (14) are shown below.
Bis (3-triethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3- Triethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) benzylamine, bis (triethoxysilylmethyl) methylamine, bis (2-triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propyl Examples thereof include amines, bis (2-triethoxysilylethyl) propylamine, and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds.

Specific examples of the compound represented by the formula (15) are shown below.
Examples include tris (triethoxysilylmethyl) amine, tris (2-triethoxysilylethyl) amine, tris (3-triethoxysilylpropyl) amine, and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds.

(Denaturation reaction)
The modification reaction of the conjugated diene polymer using the above-described modifier will be described.
The above modifiers may be used alone or in combination of two or more.
The reaction temperature, reaction time, etc. when the above-mentioned modifier is reacted with the polymerization active terminal of the conjugated diene polymer are not particularly limited, but the reaction is performed at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. It is preferable to make it.
In the above-described modifier, the total number of moles of alkoxy groups bonded to silyl groups in the added modifier is in the range of 1 to 5 times the total number of moles of lithium contained in the above-described polyfunctional anionic polymerization initiator. It is preferable to add so that it may become the range of 1.5 to 3 times, It is more preferable to add so that it may become the range of 1.5 to 2.5 times, It is further more preferable.

From the viewpoint of obtaining a predetermined modification rate and leaving one or more alkoxy groups at the end of the modified conjugated diene-based molecular chain, the modifier is a total of alkoxy groups bonded to silyl groups in the added modifier. The number of moles is preferably 1 or more times the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above, and more preferably 5 times or less from the viewpoint of cost.
The content of the polymer having a functional group component in the modified conjugated diene polymer, that is, the modification rate is low when the composition using the modified conjugated diene polymer of this embodiment is a vulcanized product. In order to obtain a good balance between loss and wet skid resistance and to obtain practically sufficient wear resistance and fracture characteristics, it is preferably 78% by mass or more, and 86% by mass or more. More preferably, it is more preferably 90% by mass or more.

The modification rate is to obtain a modification rate of 78% by mass or more as described above by controlling the concentration of allenes and acetylenes which are impurities in the conjugated diene compound, the treatment method thereof, and the polymerization temperature. Can do.
As a method for measuring the content of the polymer having a functional group component, that is, the modification rate, a measurement method by chromatography capable of separating the functional group-containing modified component and the non-modified component is preferable.
As a measurement method by this chromatography, a gel permeation chromatography (GPC) column using a polar substance such as silica adsorbing a functional group component as a filler is used, and the internal standard of the non-adsorbed component is quantified by comparison. The method is preferred.

The weight average molecular weight (GPC measurement: polystyrene conversion) of the modified conjugated diene copolymer in the present embodiment is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,000,000 in consideration of processability and physical properties. 10,000 to 500,000 is more preferable.
When a conjugated diene polymer is polymerized by a batch process, a plurality of peaks are observed in the molecular weight distribution of GPC. The peak on the lowest molecular weight side is mainly considered to be a component generated by polymerization initiated by a monofunctional component in the polyfunctional initiator mixture. The more the polyfunctional component, the better the physical properties such as low hysteresis loss and wear resistance, but the workability deteriorates. In this case, the peak area on the lowest molecular weight side may be 20 to 50%. preferable.
By adjusting the molar ratio of the polyvinyl aromatic compound and the organolithium compound in preparing the polyfunctional anionic polymerization initiator and the addition amount of the modifier within the aforementioned range, the lowest molecular weight as described above. The peak area on the side can be 20 to 50%.

After performing the modification reaction of the conjugated diene polymer with the above-described modifier, a reaction terminator may be added to the polymer solution as necessary.
As the reaction terminator, usually, alcohols such as methanol, ethanol and propanol; organic acids such as stearic acid, lauric acid and octanoic acid: water and the like can be used.
In addition, after the modification reaction of the conjugated diene polymer, the metals contained in the polymer may be decalcified as necessary.
As a deashing method, for example, a method is used in which water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide is brought into contact with a polymer solution to extract metals, and then the aqueous layer is separated. .
Further, after the modification reaction of the conjugated diene polymer, an antioxidant may be added to the polymer solution. Examples of the antioxidant include phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers and the like.

As a method for obtaining the modified conjugated diene polymer in the present embodiment from the polymer solution, a conventionally known method can be applied.
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. A method, a method of directly devolatilizing with a drum dryer or the like can be applied.

[Modified Conjugated Diene Polymer Composition]
The modified conjugated diene polymer composition of the present embodiment is 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer described above when the total rubber component is 100 parts by mass. On the other hand, the silica type inorganic filler shall contain 0.5-300 mass parts.

(Silica-based inorganic filler)
As the silica-based inorganic filler contained in the modified conjugated diene-based polymer composition of the present embodiment, solid particles having SiO ₂ or Si ₃ Al as a main component of a structural unit can be used.
Examples thereof include inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, and the like.
Further, 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, and silica is more preferable.
As silica, dry silica, wet silica, synthetic silicate silica, and the like can be used. Among them, wet silica is most preferable because it has the most remarkable effect of improving fracture characteristics and wet skid resistance.

In the modified conjugated diene polymer composition of the present embodiment, from the viewpoint of obtaining practically good abrasion resistance and fracture characteristics, the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 170 to 300 m. ² / g is preferable, and 200 to 300 m ² / g is more preferable.
As described above, the compounding amount of the silica-based inorganic filler in the modified conjugated diene polymer composition is 0.5 to 300 with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer. Although it is a mass part, 5-200 mass parts is preferable and 20-100 mass parts is more preferable.
When the compounding amount of the silica-based inorganic filler is less than 0.5 parts by mass, the additive effect of the filler is not expressed. On the other hand, when it exceeds 300 parts by mass, the dispersibility of the silica-based inorganic filler is deteriorated, This is not preferable because the processability of the composition deteriorates and the mechanical strength decreases.

(Carbon black)
Carbon black may be added to the modified conjugated diene polymer composition as a reinforcing filler other than the silica inorganic filler.
As the carbon black, carbon black of each class such as SRF, FEF, HAF, ISAF and SAF can be used, and carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a DBP oil absorption of 80 ml / 100 g is preferable.
The blending amount of carbon black is preferably 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rubber component containing 20 parts by weight or more of the modified conjugated diene polymer. Part by mass is more preferable.
In order to express performance required for applications such as tires such as dry grip performance and conductivity, 0.5 parts by mass or more is preferably added, but from the viewpoint of dispersibility, it is preferably 100 parts by mass or less.

(Metal oxide, metal hydroxide)
In addition to the silica inorganic filler and carbon black, a metal oxide or a metal hydroxide may be added to the modified conjugated diene polymer composition of the present embodiment.
The metal oxide refers to solid particles whose main component is a chemical unit M _x O _y (M is a metal atom, x and y are integers of 1 to 6), such as alumina, titanium oxide, and oxidation. Magnesium, 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 aluminum hydroxide, magnesium hydroxide, zirconium hydroxide or the like.

(Silane coupling agent)
Moreover, in the modified conjugated diene polymer composition of the present embodiment, a silane coupling agent may be contained.
The silane coupling agent has a function to close the interaction between the rubber component and the silica-based inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler. ing.
Examples of the silane coupling agent include bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, and bis- [2- (triethoxy Silyl) -ethyl] -tetrasulfide and the like.
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 compounding amount of the silane coupling agent is less than 0.1 parts by mass with respect to 100 parts by mass of the silica-based inorganic filler, an effective compounding effect cannot be obtained, and an amount exceeding 30 parts by mass is not necessary. .

The method of mixing the modified conjugated diene polymer with the silica inorganic filler, carbon black or other filler, and the silane coupling agent 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 and various compounding agents at a time and a method of mixing in multiple times can be applied.

(Vulcanizing agent)
The modified conjugated diene copolymer composition of the present embodiment may be a vulcanized composition that has been vulcanized 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.
As a vulcanization method, a conventionally known method can be applied, and the vulcanization temperature can be, for example, 120 to 200 ° C, preferably 140 to 180 ° C.

(Vulcanization accelerator, vulcanization aid)
In vulcanization, a vulcanization accelerator may be used as necessary.
As the vulcanization accelerator, conventionally known materials can be used. For example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like. Further, as the vulcanization aid, zinc white, stearic acid or the like can be used.
The usage-amount of a vulcanization accelerator shall be 0.01-20 mass parts normally with respect to 100 mass parts of rubber components containing a modified conjugated diene type polymer, and 0.1-15 mass parts is preferable.

(Rubber softener)
In order to improve processability, the modified conjugated diene polymer composition of this embodiment may be blended with 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. The rubber softener used in the present embodiment is preferably a naphthenic and / or paraffinic one.
The blending amount of the rubber softener is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and even 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. . 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 is likely to occur, and the composition surface may become sticky.

(Rubber components other than modified conjugated diene polymers)
The modified conjugated diene polymer composition in the present embodiment can be used as the rubber component by combining a rubbery polymer other than the modified conjugated diene polymer described above with the modified conjugated diene polymer.
Examples of such rubber-like polymers include conjugated diene polymers or hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof, conjugated diene compounds and vinyl compounds. Examples thereof include a block copolymer with an aromatic compound or a hydrogenated product thereof, a non-diene polymer, and natural rubber.
Specifically, 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 block copolymerized Examples thereof include styrene-based elastomers such as coalescence 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 provided with functional groups.
These rubbery polymers may be used alone or in combination of two or more.
When the above-mentioned rubbery polymer is combined with the modified conjugated diene polymer in the present embodiment and used as the rubber component, these ratios are expressed as: modified conjugated diene copolymer / rubbery polymer described above. 20 / 80-100 / 0 is preferable, 30 / 70-90 / 10 is more preferable, and 50 / 50-80 / 20 is further more preferable.

In the modified conjugated diene-based polymer composition in the present embodiment, softeners and fillers other than those described above within the range not impairing the object of the present invention, heat resistance stabilizer, antistatic agent, weather resistance stabilizer, You may use various additives, such as anti-aging agent, a coloring agent, and a lubricant.
Specific examples of the filler include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
Examples of the softening agent blended as necessary to adjust the hardness and fluidity of the target product include liquid paraffin, castor oil, and linseed oil.
Known materials can be applied as the heat resistance stabilizer, antistatic agent, weather resistance stabilizer, anti-aging agent, colorant, and lubricant.

〔tire〕
The modified conjugated diene polymer composition of this embodiment can be made into a tire by vulcanization molding according to a conventional method. Although it can be used as various tire members, it is preferably used as a tire tread material.

Hereinafter, the modified conjugated diene polymer and the composition using the same will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.
[Sample analysis method]
Analysis of samples A to I described later was performed by the method shown below.
(1) Amount of bound styrene A sample was used as a chloroform solution, and the amount of bound styrene (% by mass) was measured by absorption at UV254 nm by the phenyl group of styrene. As a measuring instrument, Shimadzu Corporation UV-2450 was used.
(2) Microstructure of butadiene moiety (1,2-vinyl bond content)
The sample was a carbon disulfide solution, the infrared spectrum was measured in the range of 600 to 1000 cm ⁻¹ using a solution cell, and the microstructure of the butadiene portion was determined from the absorbance at a predetermined wave number according to the calculation formula of the Hampton method. As a measuring instrument, JASCO Corporation FT-IR230 was used.
(3) Mooney viscosity According to JISK 6300, preheating was performed at 100 ° C. for 1 minute, and the viscosity after 4 minutes was measured. A smaller index value indicates a smaller viscosity.

(4) Molecular weight and molecular weight distribution The chromatogram was measured using GPC using three connected columns with polystyrene gel as a filler, and the molecular weight (Mw, Mn) was determined by a calibration curve using standard polystyrene. And the ratio of the lowest molecular weight peak area to the total peak area was calculated to calculate the lowest molecular weight peak area ratio.
Tetrahydrofuran (THF) was used as the eluent.
As the column, guard column: Tosoh TSKguardcolumnHHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR were used.
The molecular weight was measured using an RI detector (HLC8020 manufactured by Tosoh Corporation) under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
A sample was measured by dissolving 10 mg in 20 mL of THF and injecting 200 μL.

(5) Modification rate Applying the property that the modified component is adsorbed on a GPC column with silica gel as a filler, using a sample solution containing a sample and standard polystyrene with a molecular weight of 5000 (polystyrene does not adsorb on the column), GPC of the polystyrene-based gel column and silica-based column (guard column: DIOL 4.6 × 12.5 mm 5 micron, columns: Zorbax PSM-1000S, PSM-300S, PSM-60S, oven temperature 40 ° C., THF flow rate 0.5 ml / min. ) GPC (Tosoh CCP8020 series build-up type GPC system: AS-8020, SD-8022, CCPS, CO-8020, RI-8021) were measured using an RI detector, and the difference between them was measured. Measure the amount adsorbed on the silica column and denature I was asked.
As a sample, 10 mg was dissolved in 20 mL of THF together with 5 mg of standard polystyrene, and 200 μL was injected for measurement.
As a specific procedure, the peak area of the chromatogram using the polystyrene column is set to 100, the peak area of the standard polystyrene is P2, the peak area of the standard polystyrene is P2, and the peak area of the chromatogram using the silica column is P1. Assuming 100 as a whole, the peak area of the sample was P3, the peak area of standard polystyrene was P4, and the modification rate (%) was calculated by the formula [1- (P2 × P3) / (P1 × P4)] × 100. .

[Polyfunctional anionic polymerization initiator]
(Preparation of polyfunctional anionic polymerization initiators a to c, e, f)
After washing and drying an autoclave equipped with a stirring device and a jacket having an internal volume of 10 L and purging with nitrogen, 1,3-butadiene, cyclohexane, tetrahydrofuran and divinylbenzene subjected to a drying treatment according to the conditions shown in Table 1 below were used. Then, n-butyl lithium was added and reacted at 75 ° C. for 1 hour to prepare.
For the preparation of the polyfunctional anionic polymerization initiator, a divinylbenzene mixture (manufactured by Nippon Steel Chemical Co., Ltd.) containing m-divinylbenzene, p-divinylbenzene, ethylvinylbenzene, etc. and having a divinylbenzene concentration of 57% by mass is used. It was.
About the amount of divinylbenzene in the following Table 1, since the said commercially available divinylbenzene is a mixture, the pure amount of divinylbenzene converted excluding the content of impurities was expressed.

(Preparation of polyfunctional anionic polymerization initiator d)
In a three-way flask equipped with a magnetic stirrer, a cooling tube and a dropping funnel were set, and after nitrogen replacement, slightly pressurized nitrogen was circulated, and the inside of the system was sealed. Then, 99.0 mL (100 mmol) of a cyclohexane / n-hexane mixed solution of 0.01 mol / L of sec-butyllithium, 13.9 mL (100 mmol) of triethylamine, and 10 mL of cyclohexane were mixed and stirred at 20 ° C.
Further, 7.91 g (50 mmol) of m-diisopropenylbenzene purified by distillation under reduced pressure was added dropwise at room temperature over 3 hours, and stirring was continued for 15 hours to prepare.

[Styrene-butadiene copolymer: production of samples A to I]
[Example 1 (Sample A)]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, and 77 g of butadiene, 273 g of styrene, 4800 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -Oxolanyl) propane 0.85 g was charged into the reactor and the temperature in the reactor was maintained at 42 ° C.
The polyfunctional polymerization initiator a prepared as described above was supplied to the reactor so that the amount of lithium added was 10.5 mmol.
After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 75 ° C.
After the completion of the polymerization reaction, 5.25 mmol of bis (3-triethoxysilylpropyl) methylamine was added to the reactor, and a denaturation reaction was carried out for 5 minutes under a temperature condition of 74 ° C.
After adding 2.1 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample A) having a modifying component was obtained.

As a result of analyzing Sample A, the amount of bound styrene was 26% by mass, and the amount of bound butadiene was 74% by mass.
Sample A had a Mooney viscosity of 59.
The 1,2-bond content of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 57%.
Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 81%.
The analysis results of (Sample A) are shown in Table 2 below.

[Example 2 (Sample B), Example 3 (Sample C), Example 5 (Sample E), Comparative Example 1 (Sample G))
Table 2 below shows the types of polyfunctional anionic polymerization initiators described above, the addition amounts thereof, and the addition amounts of 2,2-bis (2-oxolanyl) propane and bis (3-triethoxysilylpropyl) methylamine. The styrene-butadiene copolymer having a modifying component (sample B), (sample C), (sample E) and (sample G) having the modified components as described above (sample A) was prepared. Got. The analysis results of (Sample B), (Sample C), (Sample E) and (Sample G) are shown in Table 2 below.

[Example 4 (Sample D)]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, and 77 g of butadiene, 273 g of styrene, 4800 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -Oxolanyl) propane 1.01 g was charged into the reactor and the temperature in the reactor was maintained at 42 ° C.
After mixing 6.3 mmol of the above-mentioned polyfunctional anionic polymerization initiator d and 4.8 mmol of n-butyllithium as a lithium addition amount, the mixture was supplied to the reactor.
At this time, the ratio of the polyvinyl aromatic compound added to the polymerization system and lithium was 0.284.
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 74 ° C.
After completion of the polymerization reaction, 6.93 mmol of bis (3-triethoxysilylpropyl) methylamine was added to the reactor, and a modification reaction was carried out at 73 ° C. for 5 minutes.
After adding 2.1 g of an antioxidant (BHT) to the polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a drier to obtain a styrene-butadiene copolymer (sample D) having a modifying component. Obtained. The analysis results of (Sample D) are shown in Table 2 below.

[Example 6 (Sample F), Comparative Example 2 (Sample H)]
In the same manner as in [Example 2 (Sample B)] described above, a styrene-butadiene copolymer was obtained using the polyfunctional anionic polymerization initiator b, and then the type of modifier was changed as shown in Table 2 below. Modification was performed to obtain styrene-butadiene copolymers (sample F) and (sample H) having a modification component. The analysis results of (Sample F) and (Sample H) are shown in Table 2 below.

[Comparative Example 3 (Sample I)]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, and 77 g of butadiene, 273 g of styrene, 4800 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -0.62 g of oxolanyl) propane was charged into the reactor and the reactor internal temperature was maintained at 42 ° C.
As a polymerization initiator, a cyclohexane solution containing 7.5 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 71 ° C.
After completion of the polymerization reaction, 4.00 mmol of 3-cyanopropyltriethoxysilane was added to the reactor, and a denaturing reaction was performed at 70 ° C. for 5 minutes.
After adding 2.1 g of an antioxidant (BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying treatment is performed by a dryer, so that a styrene-butadiene copolymer having a modifying component (sample) I) was obtained. The analysis results of (Sample I) are shown in Table 2 below.

  In addition, (Samples A to H) had a cold flow suppressing effect as compared with (Sample I) in which polymerization was started with n-butyllithium. This is because a part of the polymer after modification has a high molecular weight by using a polyfunctional initiator.

[Production of rubber composition]
[Examples 7 to 12, Comparative Examples 4 to 6]
Using the samples (sample A to sample I) shown in Table 2 as raw rubber, rubber compositions containing the raw rubbers were obtained according to the formulation shown in Table 3 below.

The rubber composition was kneaded by the following method.
Using a closed kneading machine (with an internal volume of 0.3 liters) equipped with a temperature control device, as the first stage kneading, under the conditions of a filling rate of 65% and a rotor rotational speed of 50/57 rpm, the raw rubber (sample A to sample) I, natural rubber), filler (silica, carbon black), organosilane coupling agent, process oil, zinc white, and stearic acid.
At this time, the temperature of the closed mixer was controlled, and the rubber composition was obtained at a discharge temperature (compound) of 155 to 160 ° C.

Next, as the second stage kneading, the blend obtained above was cooled to room temperature, an anti-aging agent was added, and kneaded again to improve silica dispersion. Also in this case, the discharge temperature (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
After cooling, as a third stage of kneading, sulfur and a vulcanization accelerator were added and kneaded with an open roll set at 70 ° C.
Then, it shape | molded and vulcanized with the vulcanization press for 20 minutes at 160 degreeC.
After vulcanization, the physical properties of the rubber composition were measured.
The physical property measurement results are shown in Table 4 below.
Each physical property of the rubber composition was measured by the following method.

<Bound rubber amount>
Formulation after completion of the second stage kneading step: About 0.2 gram was cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight was measured.
Then, after being immersed in toluene for 24 hours, a drying treatment was performed and the weight was measured.
The amount of rubber bound to the filler (modified conjugated diene polymer + natural rubber) was calculated from the amount of the undissolved component, and the ratio of the rubber bound to the filler to the amount of rubber in the first blend was determined.
The larger the index value, the greater the bound rubber amount.
<Formulation Mooney viscosity>
Using a Mooney viscometer, according to JIS K6300-1, the composition after the third stage kneading step was preheated at 130 ° C. for 1 minute, and then the rotor was rotated at 2 revolutions per minute to determine the viscosity after 4 minutes. It was measured. The smaller the index value, the smaller the viscosity and the better the workability.

<Tensile strength>
The vulcanized test piece was measured by the tensile test method of JIS K6251. The larger the index value, the better the fracture resistance.
<Viscoelastic parameters>
Using a viscoelasticity tester (ARES) manufactured by Rheometrics Scientific, the viscoelastic parameters of the vulcanized specimens were measured in torsion mode.
Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. The larger the index value, the better the wet grip performance.
Further, tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. The smaller the index value, the better the fuel saving performance.
Further, the difference in storage elastic modulus (G ′) between strains of 0.1% and 10% was used as an index of the Payne effect as ΔG ′. The smaller the index value, the better the dispersibility of the filler such as silica.

<Abrasion resistance>
Using an Akron abrasion tester, according to JIS K6264-2, the wear amount of the vulcanized test piece at a load of 44.1 N and 1000 revolutions was measured and indexed.
It shows that abrasion resistance is excellent, so that an index value is large.

As shown in Table 4 above, the modified conjugated diene polymer compositions of Examples 7 to 12 using (Samples A to F) described above are the compositions of Comparative Examples 5 and 6 using Samples H and I. , The amount of bound rubber in the silica compounded composition increases, the Payne effect is small and the dispersibility of silica is excellent, and the high temperature tan δ is greatly reduced, resulting in less hysteresis loss and lower tire rolling. It has been found that resistance has been realized and fuel efficiency is excellent.
In addition, since the low temperature tan δ was high, the wet skid resistance was good, and it was found that the balance between low fuel consumption and wet skid resistance was good.
In addition, the wear resistance was greatly improved and the tensile strength was good.

Furthermore, the composition of Comparative Example 4 using Sample G, which is a polymer polymerized with a polyfunctional initiator having a (polyvinyl aromatic compound / lithium) ratio higher than the range of the present invention, has a high compound viscosity and processability. Worsened. Further, due to poor kneading due to deterioration in workability, the fuel economy, wear resistance, and tensile strength were inferior to those of the examples in which the (polyvinyl aromatic compound / lithium) ratio was within the scope of the present invention. . Therefore, it was found that the (polyvinyl aromatic compound / lithium) ratio has a great influence on the balance between processability and performance.
From the above, it was found that the modified conjugated diene polymer of the present invention has a performance balance that surpasses polymers obtained by known techniques.

  The composition comprising the modified conjugated diene polymer of the present invention combined with an inorganic filler is used in the fields of automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, various industrial parts, tire applications, etc. There is a possibility to use on.

Claims (9)

Using a polyfunctional anionic polymerization initiator prepared with a molar ratio of polyvinyl aromatic compound and organolithium compound (polyvinyl aromatic compound / organolithium compound) in the range of 0.05 to 1.0,
A compound represented by the following formula (1) or (4) at a polymerization active terminal of a conjugated diene polymer obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound. Or a modified conjugated diene polymer obtained by reacting these condensates.
(In formula (1), A ¹ is a monovalent group having at least one functional group selected from cyan and sulfide , and R ¹ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. in and, R ² and R ³ are each independently a monovalent C1-20 hydrocarbon group .d is an integer of 1 to 3, if R ³ O is plural, each R ³ O it may be the not being the same or different, when R ² are a plurality, each R ² may being the same or different.)
(In the formula (4), X ¹ and X ² are alkoxy groups of halogen atom or a C 1-20, R ¹⁰ and R ¹¹ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms Each of A ² and A ³ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ⁴ is a group represented by the following formula (5), (6) or (7): When a plurality of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ² , A ³ or A ⁴ are present, they may be the same or different from each other, p and q Are each an integer of 0 to 3. h is an integer of 0 to 20, and when h is 2 or more, the plurality of repeating units represented by (A ² -A ⁴ -A ³ ) are different. In the compound represented by the formula (4), the total number of halogen atoms and the number of alkoxy groups having 1 to 20 carbon atoms may be used. The total is 5 or more.)
(In the formula (5), X ³ is .R ¹² is an alkoxy group having a halogen atom or a C1-20 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plurality of X ³ or R ¹² is When present, they may be the same or different from each other, r is an integer of 0 to 2, i is an integer of 0 to 20. When i is 2 or more, (SiX ³ _The plurality of repeating units represented by _r R ¹² _2-r ) may be different from each other, and when A ⁴ is represented by the formula (5), [p + (h × i × r) + Q] is an integer of 5 or more.)
(In Formula (6), R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When A ⁴ is represented by Formula (6), (p + q) is 5 or 6 .)
(In the formula (7), A ⁵ is a divalent hydrocarbon group of a single bond or a C 1-20, X ⁵ is .R ¹⁴ is a carbon number of an alkoxy group a halogen atom, or 1 to 20 carbon atoms It is a monovalent hydrocarbon group of 1 to 20. When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different, and s is an integer of 0 to 3. In addition, when A ⁴ is represented by the formula (7), [p + (h × s) + q] is an integer of 5 or more.)
  The modified conjugated diene polymer according to claim 1, wherein the molar ratio of the polyvinyl aromatic compound and lithium is in the range of 0.1 to 0.45.   3. The modified conjugated diene polymer according to claim 1 or 2, wherein the peak area on the lowest molecular weight side is 20 to 50% of the total area of the chromatogram in gel permeation chromatography measurement using a polystyrene gel packed column. . The molar ratio of the polyvinyl aromatic compound to the organolithium compound (polyvinyl aromatic compound / organolithium compound) is reacted in the range of 0.05 to 1.0,
Preparing a polyfunctional anionic polymerization initiator;
Using the polyfunctional anionic polymerization initiator, polymerizing a conjugated diene compound, or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
A step of reacting a compound represented by the following formula (1) or formula (4) or a condensate thereof with the polymerization active terminal of the conjugated diene polymer;
A process for producing a modified conjugated diene-based polymer.
(In formula (1), A ¹ is a monovalent group having at least one functional group selected from cyan and sulfide , and R ¹ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. in and, R ² and R ³ are each independently a monovalent C1-20 hydrocarbon group .d is an integer of 1 to 3, if R ³ O is plural, each R ³ O it may be the not being the same or different, when R ² are a plurality, each R ² may being the same or different.)
(In the formula (4), X ¹ and X ² are alkoxy groups of halogen atom or a C 1-20, R ¹⁰ and R ¹¹ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms Each of A ² and A ³ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ⁴ is a group represented by the following formula (5), (6) or (7): When a plurality of X ¹ , X ² , R ¹⁰ , R ¹¹ , A ² , A ³ or A ⁴ are present, they may be the same or different from each other, p and q Are each an integer of 0 to 3. h is an integer of 0 to 20, and when h is 2 or more, the plurality of repeating units represented by (A ² -A ⁴ -A ³ ) are different. In the compound represented by the formula (4), the total number of halogen atoms and the number of alkoxy groups having 1 to 20 carbon atoms may be used. The total is 5 or more.)
(In the formula (5), X ³ is .R ¹² is an alkoxy group having a halogen atom or a C1-20 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plurality of X ³ or R ¹² is When present, they may be the same or different from each other, r is an integer of 0 to 2, i is an integer of 0 to 20. When i is 2 or more, (SiX ³ _The plurality of repeating units represented by _r R ¹² _2-r ) may be different from each other, and when A ⁴ is represented by the formula (5), [p + (h × i × r) + Q] is an integer of 5 or more.)
(In Formula (6), R ¹³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When A ⁴ is represented by Formula (6), (p + q) is 5 or 6 .)
(In the formula (7), A ⁵ is a divalent hydrocarbon group of a single bond or a C 1-20, X ⁵ is .R ¹⁴ is a carbon number of an alkoxy group a halogen atom, or 1 to 20 carbon atoms It is a monovalent hydrocarbon group of 1 to 20. When a plurality of X ⁵ or R ¹⁴ are present, they may be the same or different, and s is an integer of 0 to 3. In addition, when A ⁴ is represented by the formula (7), [p + (h × s) + q] is an integer of 5 or more.)   The method for producing a modified conjugated diene polymer according to claim 4, wherein the molar ratio of the polyvinyl aromatic compound to the organolithium compound is in the range of 0.1 to 0.45.   The silica-based inorganic filler is contained in an amount of 0.5 to 300 parts by mass with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer according to any one of claims 1 to 3. Modified conjugated diene polymer composition.   The modified conjugated diene polymer composition according to claim 6, further comprising 0.5 to 100 parts by mass of carbon black with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer. . The modified conjugated diene polymer composition according to claim 6 or 7, wherein the silica-based inorganic filler has a nitrogen adsorption specific surface area of 170 m ² / g or more.   A tire comprising the modified conjugated diene polymer composition according to any one of claims 6 to 8.