JP2019183029A - Manufacturing method of conjugated diene rubber composition, conjugated diene rubber composition, and tire - Google Patents

Abstract

The present invention provides a conjugated diene-based polymer composition having excellent abrasion resistance without impairing rolling resistance characteristics and wet skid resistance characteristics, a method for producing the same, and a tire. A method for producing a conjugated diene-based polymer composition according to the present embodiment comprises kneading a rubber component A containing a conjugated diene-based polymer, a silica-based inorganic filler B, and a silane coupling agent C. A first kneading step, an aging step of aging the kneaded material obtained in the first kneading step at a temperature of 40 ° C. or higher, a kneaded substance obtained in the aging step, and a vulcanizing agent D. And a second kneading step of kneading. [Selection diagram] None

Description

  The present invention relates to a method for producing a conjugated diene rubber composition, a conjugated diene rubber composition, and a tire.

  In recent years, with the emphasis on resource saving and environmental measures, the level of demand for automobile tires with excellent fuel efficiency is increasing. In order to manufacture a tire excellent in fuel efficiency, it is required that the material constituting the tread, which is a contact surface with the road surface, be a material that can suppress energy loss of the tire and has low rolling resistance. From this viewpoint, a rubber material capable of forming a crosslinked rubber having excellent rolling resistance characteristics is used as a tire material.

  As a method for improving the rolling resistance characteristics of a rubber material, for example, a method of reducing the compounding amount of a reinforcing agent such as silica is known. However, when the compounding amount of the reinforcing agent is reduced, there is a problem that the hardness of the rubber composition is lowered, so that the tire is softened, wet skid resistance is deteriorated, and wear resistance is deteriorated.

  As a technique for improving wear resistance without impairing rolling resistance characteristics and wet skid resistance of a rubber compounded with an inorganic filler, for example, Patent Document 1 discloses at least two types of incompatible diene rubbers (α, β), a block polymer having a block incompatible with one of the diene rubbers β and a block compatible with both the diene rubbers, and a tread composition containing a reinforcing filler, A method is disclosed in which a block polymer, a diene rubber α and an inorganic filler are kneaded, and then a diene rubber α is added and kneaded.

Japanese Patent No. 3,392,258

  However, although the manufacturing method described in Patent Document 1 does not impair rolling resistance characteristics and wet skid resistance, characteristics that are still satisfactory with respect to wear resistance when used as a material for the base tread portion can be obtained. However, there is a problem that further improvement is necessary.

  Therefore, in the present invention, in view of the problems of the above prior art, a conjugated diene polymer composition having a high level of abrasion resistance without impairing rolling resistance characteristics and wet skid resistance characteristics, a method for producing the same, and a tire The purpose is to provide.

  As a result of intensive studies in order to solve the above-mentioned problems of the prior art, the present inventors have conjugated diene polymer composition by aging the compound at a predetermined temperature before adding sulfur or a vulcanization accelerator. The present invention has been completed by finding that the article has excellent wear resistance without impairing rolling resistance characteristics and wet skid resistance.

That is, the present invention is as follows.
(1)
A first kneading step of kneading the rubber component A containing the conjugated diene polymer, the silica-based inorganic filler B, and the silane coupling agent C;
An aging step of aging the kneaded product obtained by the first kneading step at a temperature of 40 ° C. or higher;
A method for producing a conjugated diene polymer composition, comprising: a kneaded product obtained in the aging step; and a second kneading step of kneading the vulcanizing agent D.
(2)
The production method of (1), wherein carbon black E is added and further kneaded before and / or after the aging step.
(3)
A conjugated diene polymer composition produced by the production method of (1) or (2).
(4)
(3) Conjugated diene polymer composition for tread.
(5)
A tire provided with a tread containing a crosslinked product of the conjugated diene polymer composition of (3) or (4).

  According to the present invention, it is possible to provide a conjugated diene polymer composition excellent in abrasion resistance, a method for producing the same, and a tire without impairing rolling resistance characteristics and wet skid resistance.

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

  The “rolling resistance characteristics”, “wet skid resistance”, and “abrasion resistance” referred to in the present specification are the rolling resistances when the conjugated diene polymer composition of the present embodiment is vulcanized. Characteristics, wet skid resistance, and wear resistance.

(Conjugated diene polymer composition)
First, each component used for manufacture of the modified conjugated diene polymer composition of the present embodiment will be described.

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

<Conjugated diene polymer>
From the viewpoint of improving the wear resistance of the conjugated diene polymer composition, the conjugated diene polymer contained in the rubber component used in the conjugated diene polymer composition of the present embodiment is not modified, It may be denatured. When the conjugated diene polymer composition is used for a tire tread (tread) application, it is blended into the tire by appropriately selecting a modified conjugated diene copolymer (with a functional group introduced). It is possible to improve the affinity between the filler such as silica and the copolymer, and improve tire performance such as low fuel consumption and wet grip.

  Examples of the modified conjugated diene polymer (modified conjugated diene copolymer) include those having an adsorptivity to a silica column, for example, a modified having an adsorptivity to a silica column. Examples of the conjugated diene polymer include a modified conjugated diene polymer having a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent.

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

  Although it does not specifically limit as a conjugated diene compound used in order to comprise a conjugated diene type polymer, For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1 , 3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and / or isoprene are preferable from the viewpoint of industrial availability, and 1,3-butadiene is more preferable. These may be used alone or in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinyl Xylene, vinyl naphthalene, diphenylethylene and the like can be mentioned. Among these, styrene is preferable from the viewpoint of industrial availability. These conjugated diene compounds are used singly or in combination of two or more.

  The conjugated diene polymer may be a random copolymer or a block copolymer.

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

  The block copolymer is not limited to the following, but for example, a 2 type block copolymer comprising 2 blocks, a 3 type block copolymer comprising 3 blocks, and a 4 type block comprising 4 blocks. A copolymer etc. are mentioned. For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. When expressed, it is represented by an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, or the like.

  In the above equation, the boundaries of each block need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

  The modified conjugated diene polymer in a state after the modification step is a hydrogenated modified conjugated diene polymer in which all or part of the double bonds of the conjugated diene polymer are converted to saturated hydrocarbons after the modification. There may be.

  In that case, heat resistance and weather resistance are improved, and deterioration of the product when processed at a high temperature can be prevented. As a result, it exhibits even better performance in various applications such as automotive applications.

  More specifically, the hydrogenation rate (ie, “hydrogenation rate”) of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose, and is not particularly limited. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3 to 70%, more preferably 5 to 65%, and still more preferably 10 to 60%. The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, 30 % Or less is more preferable, and 20% or less is further preferable. The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).

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

  Moreover, the amount of vinyl bonds in the conjugated diene bond unit is not particularly limited, but is preferably 10 to 75 mol%, and more preferably 25 to 65 mol%. When the vinyl bond content is in the above range, a vulcanizate having an excellent balance between low hysteresis loss and wet skid resistance and satisfying wear resistance can be obtained.

  Here, when the conjugated diene polymer is a copolymer of butadiene and styrene, vinyl in the butadiene bond unit is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The bond amount (1,2-bond amount) can be determined.

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

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

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

(Method for producing conjugated diene polymer)
The production method of the conjugated diene polymer is described below.

<Polymerization process>
The conjugated diene polymer contained in the conjugated diene polymer composition of the present embodiment has a molecular structure branched from a nitrogen-containing epoxy substituent, or a molecule branched from a nitrogen-containing alkoxysilane substituent. A modified conjugated diene polymer having a structure is mentioned as a preferred one. In the method for producing such a modified conjugated diene polymer, as the polymerization initiator, for example, a polyfunctional anionic polymerization initiator, a monofunctional anionic polymerization initiator, and the like. It is preferable to carry out the polymerization step using

[(A) Method for Producing Conjugated Diene Polymer Having Active End when Using Polyfunctional Anionic Polymerization Initiator]
The polyfunctional anionic polymerization initiator used in the step of polymerizing the conjugated diene polymer will be described.

  In this specification, the “polyfunctional anionic polymerization initiator” is an initiator having a plurality of functional groups in one molecule of the polymerization initiator, and starts the anionic polymerization starting from the plurality of functional groups. Say the agent.

  The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer can be prepared by reacting a polyvinyl aromatic compound and an organolithium compound.

  For example, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting a polyvinyl aromatic compound, an organolithium compound and a monovinyl aromatic A method of reacting a polyvinyl aromatic compound after reacting with an aromatic compound, a method of reacting an organolithium compound in the presence of two or three of a conjugated diene compound and / or a monovinyl aromatic compound and a polyvinyl aromatic compound, etc. Is mentioned.

  In particular, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting the polyvinyl aromatic compound, a conjugated diene compound and a polyvinyl compound A polyfunctional anionic polymerization initiator prepared by a method of reacting a monoorganolithium compound in the presence of is preferable.

  In order to promote and stabilize the formation of the polyfunctional anionic polymerization initiator, it is preferable to add a Lewis base to the system during the preparation.

  The polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples thereof include o, m and p-divinylbenzene, o, m and p-diisopropenylbenzene, 1 , 2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5, 4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene and the like can be mentioned. These polyvinyl aromatic compounds are used individually by 1 type or in combination of 2 or more types.

  The polyvinyl aromatic compound is particularly preferably divinylbenzene and / or diisopropenylbenzene, and may be a mixture of these o-, m-, and p-isomers.

  For the preparation of the polyfunctional anionic polymerization initiator, a conjugated diene compound and / or a monoaromatic vinyl compound may be used together with the polyvinyl aromatic compound.

  Examples of the conjugated diene compound include, but are not limited to, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1, Examples include 3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and 1,3-butadiene and / or isoprene are particularly preferable.

  Examples of the monovinyl aromatic compound include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. preferable.

  The conjugated diene compound and / or monoaromatic vinyl compound used for the adjustment of the polyfunctional anionic polymerization initiator has a polystyrene equivalent weight average molecular weight of 1,000 to 10,000 as measured by GPC. It is more preferable to add so that.

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

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

  It is also effective to add a Lewis base into the system during the preparation process of the polyfunctional anionic polymerization initiator.

  Examples of the Lewis base include, but are not limited to, tertiary monoamines, tertiary diamines, chain or cyclic ethers, and the like.

  Examples of the tertiary monoamine include, but are not limited to, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytrimethylamine, N, Examples thereof include N-dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.

  Examples of the tertiary diamine include, but are not limited to, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N , N ′, N′-tetramethylpropanediamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N Examples thereof include compounds such as' -tetramethylhexanediamine and dipiperidinoethane.

  Examples of chain ethers include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

  Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxoranyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane. 2,2-bis (2-oxolanylbutane), 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, etc. The compound of this is mentioned.

  Among Lewis bases, tertiary monoamines such as trimethylamine, triethylamine, tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine, and cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxasolanyl) Propane is preferred.

  A Lewis base is used individually by 1 type or in combination of 2 or more types.

  In addition, when a Lewis base is added when preparing a polyfunctional anionic polymerization initiator, it is preferably added within a range of 30 to 50,000 ppm with respect to the solvent used when preparing the polymerization initiator. More preferably, it is added within the range of 200 to 20,000 ppm.

  In order to fully express the effect of promoting and stabilizing the reaction, it is preferably 30 ppm or more, ensuring the degree of freedom of microstructure adjustment in the subsequent polymerization step, collecting the solvent after polymerization, and polymerizing in the purification step In consideration of separation from the catalyst, it is preferably added at 50,000 ppm or less.

  The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer before the modification of the conjugated diene polymer is such that the molar ratio of polyvinyl aromatic compound to organic lithium is polyvinyl aromatic compound / organic lithium = 0. It is preferably adjusted so as to be in the range of 0.01 to 1.0.

  The larger the amount of the polyvinyl aromatic compound used relative to the organic lithium, the more the molecular chain end to which the functional group is added by the modification reaction of the conjugated diene polymer described later when the conjugated diene polymer is a modified polymer. The ratio is increased, the affinity with silica particles and the reactivity are improved, and the balance between the low hysteresis loss and the wet skid resistance in the conjugated diene polymer composition of the present embodiment becomes good. Also, wear resistance is improved.

  On the other hand, when the amount of the polyvinyl aromatic compound used is smaller than that of the organic lithium compound, the workability during kneading can be improved, and from this viewpoint, the amount is preferably 1.0 mol or less.

  In general, when the low hysteresis loss property is improved, the Mooney viscosity of the composition tends to increase and the workability tends to deteriorate, but it is practically preferable not to increase it so much from the above viewpoint.

  From the viewpoint of improving these balances, the amount of the polyvinyl aromatic compound is more preferably in the range of 0.02 to 0.5 mol, and 0.02 to 0.1 mol of 1 mol of the organic lithium compound. A range is further preferred.

  The temperature at which the polyfunctional anionic polymerization initiator is prepared is preferably 10 ° C. or higher from the viewpoint of production, and 140 ° C. or lower from the viewpoint of suppressing side effects due to high temperature, and more preferably in the range of 35 to 110 ° C. .

  The reaction time for preparing the polyfunctional anionic polymerization initiator depends on the reaction temperature, but is in the range of 5 minutes to 24 hours.

  The conjugated diene polymer before modification of the conjugated diene polymer is obtained by an anionic polymerization reaction using the polyfunctional anionic polymerization initiator described above.

  In particular, a conjugated diene polymer having an active end obtained by a growth reaction by living anionic polymerization is more preferable. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained by a modification step described later.

  Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. As the reactor, any of known configurations such as a tank type with a stirrer and a tube type can be used.

  The polystyrene equivalent weight average molecular weight (Mw) measured by GPC of the polyfunctional anionic polymerization initiator is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 10,000. .

  The conjugated diene polymer composition of this embodiment using a conjugated diene polymer obtained by using a polyfunctional anionic polymerization initiator having a molecular weight distribution in this range has a low Mooney viscosity and a low hysteresis loss. And a vulcanizate with a good balance between wet skid resistance.

  In order to obtain a modified conjugated diene polymer, the conjugated diene polymer before modification is obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using the polyfunctional anionic polymerization initiator described above. It is done.

  If the conjugated diene compound, which is a polymerization monomer of the conjugated diene polymer, contains allenes, acetylenes, or the like as impurities, the modification reaction described later may be inhibited. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

  Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

  The polymerization reaction of the conjugated diene polymer is preferably performed in a solvent.

  Examples of the solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof.

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

  In the polymerization reaction of the conjugated diene polymer before modification of the conjugated diene polymer, a polar compound may be added.

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

  Examples of polar compounds include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2 Ethers such as oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t- Examples include alkali metal alkoxide compounds such as butyrate and sodium amylate; and phosphine compounds such as triphenylphosphine.

  Each of these polar compounds may be used alone or in combination of two or more.

  The usage-amount of a polar compound is not specifically limited, It can select according to the objective etc. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount depending on the desired vinyl bond amount as a microstructure regulator of the conjugated diene moiety of the conjugated diene polymer. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently interrupted during the copolymerization. A method of adding them may be used.

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

[(B) Method for Producing Conjugated Diene Polymer Having Polymerization Active Terminal When Using Monofunctional Anionic Polymerization Initiator]
Next, the manufacturing method of the conjugated diene polymer which has a polymerization active terminal at the time of using a monofunctional anionic polymerization initiator is demonstrated. The “monofunctional anionic polymerization initiator” refers to a polymerization initiator having one functional group in one molecule of the polymerization initiator and starting anionic polymerization starting from the functional group.

  As the monofunctional anionic polymerization initiator, a compound comprising a carbon-lithium bond is particularly preferable.

  Examples of the compound comprising a carbon-lithium bond include, but are not limited to, for example, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium. And organic lithium compounds.

  From the viewpoint of easy industrial availability and easy control of the polymerization reaction, n-butyllithium and / or sec-butyllithium is preferred.

  These organolithium compounds are used singly or in combination of two or more.

  The monofunctional anionic polymerization initiator may be used in combination with another organic alkali metal compound.

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

  An organic alkaline earth metal compound can also be used as the monofunctional anionic polymerization initiator.

  Examples of organic alkaline earth metal compounds include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with organic alkali metal compounds or other organic metal compounds.

  When the conjugated diene polymer before modification of the conjugated diene polymer is produced using the monofunctional anionic polymerization initiator, it may be a polymer of a conjugated diene compound or a copolymer with an aromatic vinyl compound. Although it does not specifically limit, It is preferable that it is a copolymer obtained by growing by an anionic polymerization reaction. In particular, the conjugated diene polymer is preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.

  Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. As the reactor, a tank type with a stirrer, a tube type or the like is used.

  Treatment of allenes and acetylenes, which are impurities, with an organometallic compound in a polymerization system before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and further has a high modification rate. Is preferable because it tends to be achieved.

  The polymerization reaction of the conjugated diene polymer is preferably performed in a solvent.

  Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof.

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

  As a polymerization initiator used in the polymerization step of the conjugated diene polymer described above, in addition to the polymerization initiator described above, “an organolithium compound having at least one nitrogen atom in the molecule” or “at least one in the molecule” A polymerization initiator system comprising a compound having two nitrogen atoms and an organolithium compound ”can be used.

  In the polymerization initiator system, an organolithium compound having at least one nitrogen atom in the molecule may be prepared in a predetermined reactor in advance, or in a reactor for performing polymerization or copolymerization described later. It may be supplied, and at the same time as or before the polymerization or copolymerization, the compound having at least one nitrogen atom in the molecule may be reacted with organolithium.

As the “compound having at least one nitrogen atom in the molecule” used in the polymerization initiator system, compounds represented by the following general formulas (1) to (3) can be used.

In formula (1), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.

In formula (2), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.

R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms. X represents a hydrogen atom, a Cl atom, a Br atom, or an I atom.

In formula (3), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₅ and R ₁₆ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R ₁₆ represent an alkyl group having 5 to 12 carbon atoms and are branched to a part thereof. You may have a structure.

In the formula (1), R ₁₀ and R ₁₁ represent, but are not limited to, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclopropyl group, a cyclohexyl group, Examples include 3-phenyl-1-propyl group, isobutyl group, decyl group, heptyl group, and phenyl group.

  The compound represented by the formula (1) is not limited to the following compounds, but examples thereof include dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di-2-ethyl. Examples include hexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine.

  The compound represented by the formula (1) is not limited to these compounds, and includes analogs thereof as long as the above conditions are satisfied.

  The compound represented by the formula (1) includes a hysteresis loss reduction of the conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the conjugated diene polymer of the present embodiment, and a chain transfer reaction described later. From the viewpoint of control, dibutylamine and dihexylamine are preferable, and dibutylamine is more preferable.

When R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, examples of the compound represented by the formula (1) include piperidine, hexamethyleneimine, azacyclooctane, , 3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydropyridine.

  The compound represented by the formula (1) is not limited to these compounds, and includes analogs thereof as long as the above conditions are satisfied.

  The compound represented by the formula (1) includes a hysteresis loss reduction of the conjugated diene polymer composition of the present embodiment, a reduction in unpleasant odor of the conjugated diene polymer of the present embodiment, and a chain transfer reaction described later. From the viewpoint of control, piperidine, hexamethyleneimine, azacyclooctane and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, piperidine and hexamethyleneimine are more preferable, and more preferable. Is piperidine.

In the formula (2), R ₁₄ preferably represents an alkyl group having 2 to 16 carbon atoms, more preferably 3 carbon atoms, from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. Represents 10 to 10 alkyl groups.

  The compound represented by the formula (2) is not limited to the following compounds. For example, 3-chloro-dimethylpropan-1-amine, 3-chloro-diethylpropan-1-amine, 3-chloro-dibutylpropane -1-amine, 3-chloro-dipropylpropan-1-amine, 3-chloro-diheptylpropan-1-amine, 3-chloro-dihexylpropan-1-amine, 3-chloropropyl-ethylhexane-1 -Amine, 3-chloro-didecylpropan-1-amine, 3-chloro-ethylpropan-1-amine, 3-chloro-ethylbutan-1-amine, 3-chloro-ethylpropan-1-amine, benzyl-3 -Chloro-ethylpropan-1-amine, 3-chloro-ethylphenethylpropan-1-amine, 3-chloro-methylphenethyl Lopan-1-amine, 1- (3-chloropropyl) piperidine, 1- (3-chloropropyl) hexamethyleneimine, 1- (3-chloropropyl) azacyclooctane, 6- (3-chloropropyl) -1 , 3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1- (3-chloropropyl) -1,2,3,6-tetrahydropyridine, 1- (3-bromopropyl) hexamethyleneimine 1- (3-iodopropyl) hexamethyleneimine, 1- (3-chlorobutyl) hexamethyleneimine, 1- (3-chloropentyl) hexamethyleneimine, 1- (3-chlorohexyl) hexamethyleneimine, 1- (3-Chlorodecyl) hexamethyleneimine.

  The compound represented by the formula (2) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  The compound represented by the formula (2) includes 3-chloro-dibutylpropan-1-amine, 1- (3-chloropropyl) from the viewpoints of reactivity and interaction with inorganic fillers such as carbon and silica. ) Hexamethyleneimine is preferred, and 1- (3-chloropropyl) hexamethyleneimine is more preferred.

In the formula (2), when R ₁₄ represents a conjugated diene polymer chain having any one repeating unit of the following formulas (4) to (6), X represents a hydrogen atom.

  When X in Formula (2) represents a hydrogen atom, the compound represented by Formula (2) is not limited to the following, but for example, N, N-dimethyl-2-butenyl-1-amine N, N-diethyl-2-butenyl-1-amine, N, N-dibutyl-2-butenyl-1-amine, N, N-dipropyl-2-butenyl-1-amine, N, N-diheptyl 2-butenyl-1-amine, N, N-dihexyl-2-butenyl-1-amine, N, N-dioctyl-2-butenyl-1-amine, N, N- (to di-2-ethyl Xyl) -2-butenyl-1-amine, N, N-didecyl-2-butenyl-1-amine, N, N-ethylpropyl-2-butenyl-1-amine, N, N-ethylbutyl-2-butenyl- 1-amine, N, N-ethylbenzyl-2-butenyl- -Amine, N, N-methylphenethyl-2-butenyl-1-amine, N, N-dimethyl-2-methyl-2-butenyl-1-amine, N, N-diethyl-2-methyl-2-butenyl- 1-amine, N, N-dibutyl-2-methyl-2-butenyl-1-amine, N, N-dipropyl-2-methyl-2-butenyl-1-amine, (N, N-diheptyl-2 -Methyl-2-butenyl-1-amine, N, N-dihexyl-2-methyl-2-butenyl-1-amine, N, N-dimethyl-3-methyl-2-butenyl-1-amine, N , N-diethyl-3-methyl-2-butenyl-1-amine, N, N-dibutyl-3-methyl-2-butenyl-1-amine, N, N-dipropyl-3-methyl-2-butenyl-1 -Amine, N, N-diheptyl-3-methyl- -Butenyl-1-amine, N, N-dihexyl-3-methyl-2-butenyl-1-amine, 1- (2-butenyl) piperidine, 1- (2-butenyl) hexamethyleneimine, 1- ( 2-butenyl) azacyclooctane, 6- (2-butenyl) 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1- (2-butenyl) -1,2,3,6 -Tetrahydropyridine, (2-methyl-2-butenyl) hexamethyleneimine, (3-methyl-2-butenyl) hexamethyleneimine.

  The compound represented by the formula (2) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  The compound represented by formula (2) is N, N-dibutyl-2-butenyl 1-amine, 1- (2-butenyl) from the viewpoint of reducing the hysteresis loss of the conjugated diene polymer composition of the present embodiment. Hexamethyleneimine is preferable, 1- (2-butenyl) piperidine and 1- (2-butenyl) hexamethyleneimine are more preferable, and 1- (2-butenyl) piperidine is more preferable.

  The compound represented by the formula (3) is not limited to the following compounds. For example, N, N-dimethyl-o-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p- Toluidine, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dipropyl-o-toluidine, N, N-dipropyl-m- Toluidine, N, N-dipropyl-p-toluidine, N, N-dibutyl-o-toluidine, N, N-dibutyl-m-toluidine, N, N-dibutyl-p-toluidine, o-piperidinotoluene, p -Piperidinotoluene, o-pyrrolidinotoluene, p-pyrrolidinotoluene, N, N, N ', N'-tetramethyltoluylenediamine, N, N, N', N'-tetraethylto Irenamine, N, N, N ′, N′-tetrapropyltoluylenediamine, N, N-dimethylxylidine, N, N-diethylxylidine, N, N-dipropylxylidine, N, N-dimethylmesidine N, N-diethylmesidin, (N, N-dimethylamino) toluylphenylmethylamine, 1- (N, N-dimethylamino) -2-methylnaphthalene, 1- (N, N-dimethylamino) -2 -Methylanthracene.

  The compound represented by the formula (3) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  The compound represented by the formula (3) is preferably N, N-dimethyl-o-toluidine from the viewpoint of reducing hysteresis loss of the modified conjugated diene polymer composition described later.

  As the polymerization initiator system, the organolithium compound combined with the above-described compound having at least one nitrogen atom in the molecule is not limited to the following, but for example, n-butyllithium, sec-butyllithium, tert-butyl Lithium, n-propyllithium and iso-propyllithium are mentioned.

The organolithium compound constituting the polymerization initiator system has at least one nitrogen atom in the molecule and can be used as a polymerization initiator for anionic polymerization from the viewpoint of improving the modification rate and improving fuel efficiency. Yes, it preferably contains an organolithium compound represented by any one of the following general formulas (7) to (10).

In formula (7), R ₁₀ and R ₁₁ are each independently selected from the group consisting of alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 14 carbon atoms, and aralkyl groups having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.

In formula (8), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure. R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms.

In formula (9), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected.

R ₁₅ and R ₁₆ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R ₁₆ represent an alkyl group having 5 to 12 carbon atoms and are branched to a part thereof. You may have a structure.

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

R ₁₈ represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.

In the formula (7), R ₁₀ and R ₁₁ represent, but are not limited to, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, siltium group, ethylpropylamino Examples thereof include a lithium group, an ethylbutylaminolithium group, an ethylbenzylaminolithium group, and a methylphenethylaminolithium group.

R ₁₀ and R ₁₁ are not limited to these, and include the similar compounds as long as the above conditions are satisfied. From the viewpoint of solubility in a solvent, reduction of hysteresis loss of the modified conjugated diene polymer composition of the present embodiment, and viewpoint of chain transfer reaction control described later, a dibutylaminolithium group and a dihexylaminolithium group are preferable, and more A dibutylamine group is preferred.

In the formula (7), when R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organolithium compound represented by the formula (7) is not limited to the following. Are, for example, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydro A pyridino lithium is mentioned. The organolithium compound represented by the formula (7) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoints of solubility of the polymerization initiator in the solvent, reduction of unpleasant odor of the modified conjugated diene polymer of the present embodiment, and suppression of chain transfer reaction, piperidinolithium, hexamethyleneiminolithium, lithium azacyclo Octane and lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, piperidinolithium or hexamethyleneiminolithium is more preferable, and piperidinolithium is more preferable. .

In the formula (8), R ₁₄ represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer chain having 1 to 20 carbon atoms.

The conjugated diene polymer chain preferably represents a conjugated diene polymer chain having a repeating unit represented by any one of the following formulas (11) to (13).

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

In addition, when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms, the organolithium compound represented by the formula (8) is not limited to the following, but for example, (3- (dimethylamino) -propyl ) Lithium, (3- (diethylamino) -propyl) lithium, (3- (dipropylamino) -propyl) lithium, (3- (dibutylamino) -propyl) lithium, (3- (dipentylamino) -propyl) lithium , (3- (dihexylamino) -propyl) lithium, (3- (dioctylamino) -propyl) lithium, (3- (ethylhexylamino) -propyl) lithium, (3- (didecylamino) -propyl) lithium, 3- (ethylpropylamino-propyl) lithium, (3- (ethylbutylamino-propyl) lithium, (3- Ethylbenzylamino) -propyl) lithium, (3- (methylphenethylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, (5- (dibutylamino) -pentyl) lithium, (6- ( And dibutylamino) -hexyl) lithium and (10- (dibutylamino) -decyl) lithium.

  The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, (3- (dibutylamino) -propyl) lithium is more preferable.

In the formula (8), when R ₁₄ represents a conjugated diene polymer chain having a repeating unit represented by the formulas (11) to (13), the organolithium compound represented by the formula (8) is as follows: Although not limited to, for example, (4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (dibutylamino) -2-butenyl) Lithium, (4- (dipropylamino) -2-butenyl) lithium, (4- (diheptylamino) -2-butenyl) lithium, (4- (dihexylamino) -2-butenyl) lithium, (4- (Dioctylamino) -2-butenyl) lithium, (4- (di-2-ethylhexylamino) -2-butenyl) lithium, (4- (didecylamino) -2-butenyl) lithium, -(Ethylpropylamino) -2-butenyl) lithium, (4- (ethylbutylamino) -2-butenyl) lithium, (4- (ethylbenzylamino) -2-butenyl) lithium, (4- (methylphenethylamino) ) -2-butenyl) lithium, (4- (dimethylamino) -2-methyl-2-butenyl) lithium, (4- (diethylamino) -2-methyl-2-butenyl) lithium, (4- (dibutylamino) -2-methyl-2-butenyl) lithium, (4- (dipropylamino) -2-methyl-2-butenyl) lithium, (4- (diheptylamino) -2-methyl-2-butenyl) lithium, ( 4- (dihexylamino) -2-methyl-2-butenyl) lithium, (4- (dimethylamino) -3-methyl-2-butenyl) lithium, (4 (Diethylamino) -3-methyl-2-butenyl) lithium, (4- (dibutylamino) -3-methyl-2-butenyl) lithium, (4- (dipropylamino) -3-methyl-2-butenyl) lithium , (4- (diheptylamino) -3-methyl-2-butenyl) lithium and (4- (dihexylamino) -3-methyl-2-butenyl) lithium.

  The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity as a polymerization initiator and the viewpoint of chain transfer reaction control described later, 4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (Dibutylamino) -2-butenyl) lithium is preferred, and (4- (dibutylamino) -2-butenyl) lithium is more preferred.

In the formula (8), when R ₁₂ and R ₁₃ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organic lithium compound represented by the formula (8) is limited to the following: For example, (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneiminyl) propyl) lithium, (3- (heptamethyleneiminyl) propyl) lithium, (3- (octamethylene) (Minyl) propyl) lithium, (3- (1,3,3-trimethyl-6-azabicyclo [3.2.1] octanyl) propyl) lithium, (3- (1,2,3,6-tetrahydropyridinyl) ) Propyl) lithium, (2- (hexamethineleniminyl) ethyl) lithium, (4- (hexamethineleniminyl) butyl) lithium, (5- (hexamethinelenine) (Minyl) pentyl) lithium, (6- (hexamethineleniminyl) hexyl) lithium, (10- (hexamethyleneleniminyl) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (Hexamethineleniminyl) -2-butenyl) lithium, (4- (heptamethyleneiminyl) -2-butenyl) lithium, (4- (octamethyleneiminyl) -2-butenyl) lithium, (4- ( 1,3,3-trimethyl-6-azabicyclo [3.2.1] octanyl) -2-butenyl) lithium, (4- (1,2,3,6-tetrahydropyridinyl) -2-butenyl) lithium , (4- (hexamethineleniminyl) -2-methyl-2-butenyl) lithium, (4- (hexamethineleniminyl) -3-methyl-2-butenyl) Lithium and the like.

  The organolithium compound represented by the formula (8) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, and from the viewpoint of chain transfer reaction control to be described later, (3- (piperidinyl) propyl) lithium, (3- (hexamethineleniminyl) propyl ) Lithium, (3- (1,2,3,6-tetrahydropyridinyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyneleniminyl) -2- Butenyl) lithium is preferred, more preferably (3- (hexamethyleneleniminyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyleneleniminyl) -2-butenyl) ) Lithium is preferred, and (4- (piperidinyl) -2-butenyl) lithium is more preferred.

  The organolithium compound represented by the formula (9) is not limited to the following, but examples thereof include N, N-dimethyl-o-toluidinolithium, N, N-dimethyl-m-toluidinolithium, N, N-dimethyl-p-toluidinolithium, N, N-diethyl-o-toluidinolithium, N, N-diethyl-m-toluidinolithium, N, N-diethyl-p-toluidino Lithium, N, N-dipropyl-o-toluidinolithium, N, N-dipropyl-m-toluidinolithium, N, N-dipropyl-p-toluidinolithium, N, N-dibutyl-o-to Louisinolithium, N, N-dibutyl-m-toluidinolithium, N, N-dibutyl-p-toluidinolithium, o-piperidinotruenolithium, p-piperidinotruenolithium, o-pyrrole Notorenolithium, p-pyrrolidinotoluene, N, N, N ′, N′-tetramethyltoluylenediaminolithium, N, N, N ′, N′-tetraethyltoluylenediaminolithium, N, N, N ′, N'-tetrapropyltoluylenediaminolithium, N, N-dimethylxylidinolithium, N, N-diethylxylidinolithium, N, N-dipropylxylidinolithium, N, N-dimethylmesidinolithium, N, N -Diethylmesidinolithium, (N, N-dimethylamino) toluylphenylmethylaminolithium, 1- (N, N-dimethylamino) -2-methylnaphthalenolithium, 1- (N, N-dimethylamino) -2 -Methylanthracenolithium.

  The organolithium compound represented by the formula (9) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of polymerization activity, N, N-dimethyl-o-toluidinolithium is more preferable.

  The organolithium compound represented by the formula (10) is not limited to the following compounds. For example, 2- (2-methylpiperidinyl) -1-ethyllithium (for example, trade name “AI” manufactured by FMC Co., Ltd.) -250 ").

  The organolithium compound represented by the formula (10) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  When the conjugated diene polymer is a modified product, before the polymerization step of the conjugated diene polymer in the state before the modification, organolithium having at least one nitrogen atom in the molecule in advance as the above-described polymerization initiator The compound may be prepared and the method is prepared by any known method.

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

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

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

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

  From the viewpoint of reactivity and safety, the compound represented by the formula (A) is 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6. One selected from the group consisting of -chlorohexane and 1-bromo-10-chlorodecane is preferred, more preferably 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, and 1-bromo-6- It is one selected from the group consisting of chlorohexane.

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

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

The organolithium compound represented by formula (8) having at least one nitrogen atom in the molecule is a conjugated diene in which R ₁₄ has a repeating unit represented by any one of formulas (11) to (13). When it represents a polymer chain, it is synthesized by the following steps (I) to (IV).
(I) A compound represented by the formula (2) and an organic lithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.
(II) The obtained lithium amide compound is reacted with butadiene or isoprene in a hydrocarbon solvent.
(III) Alcohol is added to deactivate lithium and the resulting product is distilled under reduced pressure.
(IV) The product obtained by distillation is reacted with an organolithium compound in a hydrocarbon solvent.

  The reaction temperature of step (I) in which lithium amide is prepared using the compound represented by the formula (2), the organic lithium compound, and the hydrocarbon solvent is as described above.

  The alcohol used in step (III) can be a general one, but preferably has a low molecular weight, for example, one selected from the group consisting of methanol, ethanol, and isopropanol, more preferably ethanol. It is.

  The reaction temperature in step (IV) is 0 ° C. or higher and 80 ° C. or lower, preferably 10 ° C. or higher and 70 ° C. or lower.

  When preparing the organolithium compound, a polar compound may be added to the system. There is a tendency to promote the formation and solubilization in a hydrocarbon solvent. Examples of the polar compound include, but are not limited to, the following: tertiary monoamines, tertiary diamines, chained or cyclic ethers.

  The tertiary monoamine is not limited to the following, but examples include trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, N- Examples thereof include dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.

  The tertiary diamine is not limited to the following, but examples thereof include N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropanediamine, N, N, N', N'-tetramethyldiaminobutane, N, N, N ', N'-tetramethyldiaminopentane, N, N, N', N'- Examples include tetramethylhexanediamine, dipiperidinopentane, and dipiperidinoethane.

  Examples of the chain ether include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

  Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, 2 , 2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane.

  Among polar compounds, tertiary monoamines such as trimethylamine and triethylamine; tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine, cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxolanyl) propane Is preferred. A polar compound is used individually by 1 type or in combination of 2 or more types.

  When adding a polar compound when preparing an organolithium compound that is a polymerization initiator, it is preferably added within the range of 30 ppm to 50,000 ppm by mass with respect to the solvent used when preparing, It is more preferable to add in the range of mass ppm or more and 20,000 mass ppm or less. Addition of 30 mass ppm or more is preferable in order to fully express the effects of reaction promotion and solubilization in a solvent, ensuring the degree of freedom of microstructure adjustment in the polymerization step, and recovering the solvent after polymerization. Considering the separation from the polymerization solvent in the purification step, it is preferable to add at 50,000 mass ppm or less.

  When the conjugated diene polymer is a modified product, the conjugated diene polymer before the modification is the above-described various polymerization initiators, preferably an organolithium compound having at least one nitrogen atom in the molecule, or at least 1 It is obtained by polymerizing with a conjugated diene compound using a polymerization initiator system containing a compound having two nitrogen atoms and an organolithium compound, or by copolymerizing a conjugated diene compound and an aromatic vinyl compound.

  In the polymerization step, an organolithium compound having at least one nitrogen atom in the molecule is prepared in advance in a predetermined reactor, and polymerization of the conjugated diene compound or copolymerization of the conjugated diene compound and the aromatic vinyl compound is performed. The polymerization reaction may be carried out by supplying to a reactor that performs the above, or the above-mentioned compound having at least one nitrogen atom in the molecule and the organolithium compound are mixed and prepared using a static mixer or in-line mixer. A polymerization reaction may be performed. When the organic lithium compound having at least one nitrogen atom in the molecule as described above is used as the polymerization initiator, the compound is used singly or in combination of two or more.

  A conjugated diene polymer having a functional group containing a nitrogen atom at a polymerization initiation terminal is obtained by using a polymerization initiator system containing an organic lithium compound and a compound having at least one nitrogen atom in the molecule. It is obtained by a polymerization process in which a conjugated diene compound and an aromatic vinyl compound are copolymerized.

  The polymerization step of the conjugated diene polymer may be carried out by either a batch type or a continuous type polymerization method. However, a high modification rate, a high molecular weight, and a viewpoint of stably producing a highly branched conjugated diene polymer. Therefore, it is preferable to perform polymerization in a continuous mode, and it is more preferable to perform polymerization in a continuous mode in one reactor or two or more connected reactors.

  At this time, in order to make the modification rate 75% by mass or more and MSR (stress relaxation) 0.45 or less, for example, the polymerization temperature is 45 ° C. or more and 80 ° C. or less and the solid content (solid content) is 16. It is preferable to make it 0 mass% or less.

  In order to make the modification rate 78% by mass or more and the MSR 0.45 or less, the polymerization temperature should be controlled in the range of 50 ° C. or more and 80 ° C. or less, and the solid content should be 16.0% by mass or less. preferable.

  In order to make the modification rate 80% by mass or more and MSR 0.44 or less, it is preferable to control the polymerization temperature in the range of 50 ° C. or more and 80 ° C. or less and to make the solid content 16.0% by mass or less. The feed composition of the organolithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent.

  In order to achieve a modification rate of 85% by mass or more and an MSR of 0.43 or less, the polymerization temperature is controlled in the range of 50 ° C. or more and 78 ° C. or less, the solid content is 16.0% by mass or less, and organic The feed composition of the lithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent.

  In order to make the modification rate 88% by mass or more and MSR 0.42 or less, the polymerization temperature is 55 ° C. or more and 76 ° C. or less, the solid content is 15.0% by mass or less, and the feed composition of the organolithium compound Is preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent.

  More preferably, from the viewpoint of appropriately controlling the chain transfer reaction described below, achieving a modification rate of 90% by mass or more and an MSR of 0.40 or less, that is, achieving a high modification rate, high molecular weight, and high branching. Polymerization, the polymerization temperature is 60 ° C. or more and 72 ° C. or less, the solid content is 14.0% by mass or less, the organolithium compound is continuously added, and the feed composition of the organolithium compound is relative to the hydrocarbon solvent. Is preferably 0.00070 mol / L or less.

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

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

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

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

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

  In the polymerization step, from the viewpoint of chain transfer reaction control, the solid is a content of the conjugated diene compound and the aromatic vinyl compound, and the total mass of the solvent, such as the conjugated diene compound and the aromatic vinyl compound. The content (also referred to as “monomer concentration”) is preferably 16% by mass or less, more preferably 15% by mass or less, and still more preferably 14% by mass or less. The upper limit of the solid content is not particularly limited, but is preferably 12.5% by mass or more.

  In the polymerization step, from the viewpoint of chain transfer reaction control and suppression of active terminal deactivation, the polymerization method is continuous, the polymerization temperature is 45 ° C. or higher and 80 ° C. or lower, and the solid content is 16% by mass or less. Is preferred.

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

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

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

  The conjugated diene compound, the aromatic vinyl compound, and the polymerization solvent are each treated alone or mixed with these mixed solutions in advance before being subjected to a polymerization reaction by reacting the organometallic compound with allenes and acetylenes that are impurities. It is preferable to keep it.

  Thereby, inhibition of polymerization by impurities can be prevented, the active terminal amount of the polymer becomes high, a sharper molecular weight distribution (Mw / Mn) can be achieved, and a higher modification rate tends to be achieved.

  In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. Thereby, an aromatic vinyl compound can be copolymerized randomly with a conjugated diene compound, and it tends to be used as a vinylating agent for controlling the microstructure of the conjugated diene part. It is also effective in improving the polymerization rate.

  Examples of polar compounds include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl). ) Ethers such as propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t-butylate, Examples include alkali metal alkoxide compounds such as sodium amylate; and phosphine compounds such as triphenylphosphine.

  These polar compounds are used singly or in combination of two or more.

  The usage-amount of a polar compound is not specifically limited, Although it can select according to the objective etc., it is preferable that they are 0.01 mol or more and 100 mol or less with respect to 1 mol of polymerization initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of conjugated diene compounds and aromatic vinyl compounds, and tend to be used to adjust the distribution of aromatic vinyl compounds and adjust the amount of styrene block It is in.

  As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently interrupted during the copolymerization. The method of adding automatically is mentioned.

  When the conjugated diene polymer is a modified product, the amount of bound conjugated diene in the conjugated diene polymer before the modification is not particularly limited, but as described above, it is 50% by mass or more and 100% by mass or less. Is preferable, and more preferably 60% by mass or more and 80% by mass or less.

  Further, the amount of bonded aromatic vinyl in the conjugated diene polymer is not particularly limited, but is preferably 0% by mass or more and 50% by mass or less, as described above, and is 20% by mass or more and 40% by mass or less. Is more preferable.

  If the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate that has a better balance between low hysteresis loss and wet skid resistance, and that is more satisfactory in wear resistance and fracture strength can be obtained. It tends to be possible. Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it measures according to the method as described in the Example mentioned later.

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

  The conjugated diene polymer before modification of the conjugated diene polymer is not limited to the following, for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, A butadiene-isoprene-styrene random copolymer may be mentioned.

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

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

  As described above, when the microstructure (each bond amount in the conjugated diene copolymer) is in the above range, and the glass transition temperature of the copolymer is in the range of −45 ° C. or higher and −15 ° C. or lower. Further, a superior vulcanizate can be obtained due to the balance between low hysteresis loss and wet skid resistance.

  Regarding the glass transition temperature, in accordance with ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature. Specifically, it is measured by the method described in the examples described later.

  As described above, when the conjugated diene polymer used in this embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, the number of blocks in which 30 or more aromatic vinyl units are linked is small. It is preferable that it is what is or does not exist.

  Specifically, when the conjugated diene polymer is a butadiene-styrene copolymer, the method described in Kolthoff's method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In the known method for analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are chained is preferably 5.0% by mass with respect to the total amount of the polymer. Hereinafter, it is more preferably 3.0% by mass or less.

(Modification process)
After obtaining a conjugated diene polymer having a polymerization active terminal by the method described above, a predetermined modifier is reacted with the polymerization active terminal, and a modification step is performed, thereby modifying the conjugated diene polymer. (In this specification, it may be described as a modified conjugated diene polymer).

  Preferably, a compound having a nitrogen atom in the molecule and having two or more epoxy groups (modifier), or a compound having an alkoxy group bonded to a silyl group in the molecule and having a nitrogen atom, which will be described later A modified conjugated diene polymer is obtained by performing a modification step of reacting (modifier).

  In the modification step, the epoxy group of the compound having a nitrogen atom in the molecule and having an epoxy group (modifier) reacts with the polymerization active terminal of the conjugated diene polymer, so that the conjugated diene polymerization active terminal and A bond can be formed between the oxygen atoms of the ring-opened epoxy group.

  In addition, the alkoxy group bonded to the silyl group of the compound (modifier) having an alkoxy group bonded to the silyl group in the molecule reacts with the polymerization active terminal of the conjugated diene polymer, A bond between the terminal of the conjugated diene polymer and Si can be formed. As a result, the modified conjugated diene polymer has a molecular structure branched from a nitrogen-containing epoxy substituent or a nitrogen-containing alkoxysilane substituent.

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

In the general formula (14), R ¹⁹ and R ²⁰ are each a hydrocarbon group having 1 to 10 carbon atoms or an ether group and / or a hydrocarbon group having 1 to 10 carbon atoms having a tertiary amine, R ²¹ and R ²² are , Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms having an ether and / or a tertiary amine, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, or an ether, It is a C1-C20 hydrocarbon group which has at least 1 sort (s) of tertiary amine, epoxy, carbonyl, and halogen, and k is 1-6.

  The modifier represented by the general formula (14) is preferably a compound having k of 2 or 3, for example, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane. Tetraglycidyl-1,3-bisaminomethylcyclohexane and the like.

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

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

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

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

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

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

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

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

In general formula (G), Z < ⁵ > shows a single bond or a C1-C20 hydrocarbon group, and i shows the integer of 1-10. When there are a plurality of Z ^{5 s} , they are independent of each other.
The modifier represented by the general formula (15) is not limited to the following, and examples thereof include 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- ( Diethoxyethylsilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) propyl] -3-ethylimidazo Lysine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxy) Silyl) propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) propyl] -1 Ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine, (2- {3- [3- (trimethoxysilyl) ) Propyl] tetrahydropyrimidin-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (dimethoxymethylsilyl) propyl] -4- (Trimethylsilyl) piperazine, 1- [3- (tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [ -(Dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxysilyl) Butyl] -4- (trimethylsilyl) piperazine and the like.

  Of these, 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (tri Methoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) Piperazine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine are preferred, and 1- [ 3- (triethoxysilyl) propyl] -4-methylpiperazine and 1- [3- (triethoxysilyl) propi ] -4 least one selected from the group consisting of (trimethylsilyl) piperazine are preferable.

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

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

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

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

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

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

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

  In the modifier of the general formula (17), Y is preferably represented by the general formula (D) or the general formula (E), and f is preferably 0. Such a modifier tends to be easily available, and tends to be more excellent in wear resistance and low hysteresis loss performance when a modified conjugated diene polymer is used as a vulcanizate.

  Such modifiers are not limited to the following, but include, for example, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]. Amine, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2- Silacyclopentane) propyl] -1,3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-tri Methoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisamino Tylcyclohexane, tris (3-trimethoxysilylpropyl) -methyl-1,3-propanediamine, and bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3- Trismethoxysilylpropyl) -methyl-1,3-propanediamine.

  In the modifier of the general formula (17), Y is represented by the general formula (D) or the general formula (E), f represents 0, and in the general formula (D) or the general formula (E), i is 2 What shows the integer of -10 is more preferable. Thereby, it exists in the tendency for the abrasion resistance and low hysteresis loss performance when vulcanized to become more excellent.

Such modifiers are not limited to the following, but include, for example, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, and N ^1- (3- (bis (3- (trimethoxy silyl) propyl) amino) propyl) -N ¹ - methyl -N ³ - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N ³ - (3- (trimethoxysilyl) propyl) -1,3-propanediamine.

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

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

  In the above-described modifiers other than the general formula (17), the total number of moles of epoxy groups in the compound or the total number of moles of alkoxy groups bonded to the silyl group is 0.8 to the number of moles of anionic polymerization initiator added. The range is preferably 3 times, more preferably 1 to 2.5 times, and even more preferably 1 to 2 times.

  The resulting modified conjugated diene polymer is preferably 0.8 times or more in order to obtain a sufficient modification rate, and the polymer ends are coupled to improve the extrusion processability to obtain a branched polymer component. In addition to the above, it is preferably 3 times or less from the viewpoint of the modifier cost.

  In the method for producing a modified conjugated diene polymer, a deactivation agent, a neutralizing agent, and the like may be added to the polymer solution as necessary after the modification reaction.

  Examples of the quenching agent include water; alcohols such as methanol, ethanol, and isopropanol. Examples of the neutralizing agent include organic acids such as stearic acid, oleic acid and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas and the like.

  The modified conjugated diene polymer is preferably added with a rubber stabilizer from the viewpoint of preventing gel formation in the finishing step after polymerization and improving the stability during processing. The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4 ′ -Hydroxy-3 ', 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis [(octylthio) methyl] phenol and the like are preferable.

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

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

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

Examples of the modified conjugated diene polymer having a molecular structure branched from a nitrogen-containing alkoxysilane substituent as produced above include, for example, the following general formula (19), general formula (20), The compound etc. which are shown to General formula (21) are mentioned.

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

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

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

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

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

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

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

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

The conjugated diene polymer composition of the present embodiment may contain other rubber-like polymers as rubber components within the range satisfying the characteristics of the present embodiment, in addition to the conjugated diene polymer described above.
Such a rubbery polymer is not limited to the following, but for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a Examples thereof include a hydrogenated product, a block copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, a non-diene polymer, and natural rubber.

  Specific examples include natural rubber, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, and styrene-butadiene rubber or hydrogenated product thereof. Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin-based elastomers, butyl rubber, brominated butyl rubber, Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber and the like can be mentioned.

  The various rubber-like polymers described above may be modified rubbers to which functional groups having polarity such as hydroxyl groups and amino groups other than conjugated diene polymers are added. The weight average molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 1,500,000, from the viewpoint of the balance between performance and processing characteristics. Also, so-called liquid rubber having a low molecular weight can be used. These rubber-like polymers are used individually by 1 type or in combination of 2 or more types.

<Silica-based inorganic filler B (component B)>
The conjugated diene polymer composition of this embodiment contains a silica-based inorganic filler B (component B).

  The silica-based inorganic filler B (component B) may be any “silica-based inorganic filler” blended in a tire, and is particularly used for improving the strength of the rubber composition for base treads. A “silica-based inorganic filler” can be widely used as an essential component of the conjugated diene polymer composition of the present embodiment.

  The content of the silica-based inorganic filler B (component B) is not limited as long as the reinforcing effect of the conjugated diene polymer composition of the present embodiment can be obtained. From 1 to 300 parts by mass is preferable with respect to parts, from the viewpoint of toughness and workability, more preferably from 5 to 150 parts by mass, and even more preferably from 10 to 100 parts by mass.

The silica-based inorganic filler B used in the conjugated diene polymer composition of the present embodiment is not particularly limited, and a known one can be used, and includes SiO ₂ or Si ₃ Al as a structural unit. Solid particles are preferable, and SiO ₂ or Si ₃ Al is more preferable as a main component of the structural unit.

  Here, the main component refers to a component contained in the silica-based inorganic filler B by 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more.

  Specific examples of the silica-based inorganic filler B include inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable.

  Examples of the dry silica include those obtained by reacting purified silicon tetrachloride in a high-temperature flame and having higher purity, finer particles, and extremely low moisture compared to the wet type. It is widely used as a raw material for fillers, resin thickeners, reinforcing agents, powder fluidizers and ceramics.

  As wet silica, for example, sodium silicate using silica sand as a raw material, neutralizing the aqueous solution to deposit silica, filtering and drying, a fluffy and light white powder is given in appearance. In general, it is used as a reinforcing filler for synthetic rubber, prevention of powdering and consolidation of liquids such as agricultural chemicals, prevention of back-through of printing ink for lightweight paper, paint, ink thickening and anti-sagging, thermal insulation, and abrasive. .

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

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

<Silane coupling agent C (component C)>
In the conjugated diene polymer composition of this embodiment, silica-based inorganic filler B (component B) is blended.

  Although the silane coupling agent is not limited to the following, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik Degussa: Si363], Momentive NXT-Z30, NXT-Z45, Silane coupling agents containing mercapto groups such as NXTZ60, NXT silane, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis -[2- (triethoxysilyl -Ethyl] -tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis ( 2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N , N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxy Methylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like.

  In particular, bis- [3- (triethoxysilyl) -propyl] -disulfide, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik Degussa: Si363], Momentive's NXT-Z30, NXT-Z45, NXTZ60, silane coupling agents containing mercapto groups such as NXT silane, bis- [3- (triethoxysilyl) -propyl] -tetra Sulfide is preferred because of its high reinforcing effect.

  These silane coupling agents C can be used alone or in combination of two or more.

  The blending amount of the silane coupling agent C is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and 1 to 15 parts by mass with respect to 100 parts by mass of the silica-based inorganic filler B described above. Is more preferable. When the blending amount of the silane coupling agent C is within the above range, the addition effect of the silane coupling agent C can be made more remarkable.

<Vulcanizing agent D (component (D))>
The conjugated diene polymer composition of the present embodiment has an effect that wear resistance is particularly excellent without impairing rolling resistance characteristics and wet skid resistance, but this effect is achieved by adding a vulcanizing agent. It can be confirmed after vulcanization. The vulcanization process needs to be performed after the aging process. If aging is performed after the vulcanizing agent is added, vulcanization proceeds, and molding failure may occur during molding. However, if aging is performed prior to the vulcanization step, this problem can be suppressed.

  As the vulcanizing agent D, 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 usage-amount of the vulcanizing agent D is 0.01-20 mass parts normally with respect to 100 mass parts of rubber components A containing a modified conjugated diene type polymer, and 0.1-15 mass parts is preferable. A conventionally known method can be applied as the vulcanization method, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

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

<Carbon black E>
The conjugated diene polymer composition of the present embodiment preferably further contains carbon black E from the viewpoint of the reinforcing effect, and 0.5 to 100 parts by mass of carbon black E with respect to 100 parts by mass of the rubber component. More preferred is

The carbon black E is not particularly limited, and for example, carbon black of each class such as SRF, FEF, HAF, ISAF, SAF, etc. can be used. Among these, the nitrogen adsorption specific surface area has a nitrogen adsorption specific surface area of 50 m ² / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or more from the viewpoint of extrusion moldability and rolling resistance characteristics. Certain carbon blacks are preferred.

  The blending amount of the carbon black is 0.5 to about 100 parts by mass of the conjugated diene polymer A from the viewpoint of further developing the rolling resistance characteristics by adding the silica-based inorganic filler B and further improving the extrusion processability. 100 mass parts is preferable, 3-100 mass parts is more preferable, and 5-50 mass parts is further more preferable.

  Next, the manufacturing method of the conjugated diene polymer composition of this embodiment is demonstrated.

<Method for Producing Conjugated Diene Polymer Composition>
The manufacturing method of the conjugated diene polymer composition of this embodiment includes a rubber component A (component A) containing a conjugated diene polymer, a silica-based inorganic filler B (component B), and a silane coupling agent C ( A first kneading step for kneading component C), an aging step for aging the kneaded product obtained by the first kneading step at a temperature of 40 ° C. or higher, and a kneaded product obtained by the aging step; And a second kneading step of kneading the vulcanizing agent D (component D).

  In the first kneading step, component A, component B and component C may be kneaded all at once, or each component may be added sequentially and kneaded.

(First kneading step)
Although the kneading | mixing temperature in a 1st kneading process is not specifically limited, For example, the range of 120-170 degreeC is preferable. When the kneading temperature is within the above range, the reaction rate between the component B and the component C is improved, and the dispersibility can be enhanced. The kneading temperature is preferably selected according to the type of component C.

  For example, when Component C has 3 or more sulfur atoms in its molecular structure, the kneading temperature is preferably in the range of 120 to 160 ° C, more preferably in the range of 140 to 150 ° C.

  Although it does not specifically limit as a silane coupling agent which has three or more sulfur atoms in molecular structure, Specifically, bis- (2- (triethoxysilyl) -ethyl) -tetrasulfide and bis- ( 3- (triethoxysilyl) -propyl) -tetrasulfide and the like.

  For example, when component C has 1 to 2 sulfur atoms in its molecular structure, the kneading temperature is preferably in the range of 140 to 170 ° C, more preferably in the range of 150 to 160 ° C. preferable.

  The silane coupling agent having 1 to 2 sulfur atoms in the molecular structure is not particularly limited, and specific examples include bis- (3- (triethoxysilyl) -propyl) -disulfide.

  In the first kneading step, the kneading time after reaching the desired temperature, for example, 150 to 160 ° C. or 140 to 150 ° C. selected as described above, is 2 to 8 during kneading. It is preferable to set it as minutes, and it is more preferable to set it as 2 to 5 minutes. Thereby, the balance of each physical property of a conjugated diene polymer composition can be raised more.

  In the first kneading step, at least components A, B and C may be added and kneaded, and other components other than components A, B and C may be further added and kneaded. Examples of other components include extender oil, carbon black, vulcanization aid, lubricant, anti-aging agent, metal oxide or metal hydroxide, rubber softener, and additive. These other components may be kneaded together with component A, component B, and component C, or each component may be added sequentially and kneaded. In the manufacturing method of the present embodiment, in the second kneading step, the other components may be added and kneaded.

(Extension oil)
In the first kneading step, it is preferable to further add and extend the kneading oil. This tends to further improve the processability of the resulting conjugated diene polymer composition. Examples of the extending oil include aroma oil, naphthenic oil, and paraffin oil. These extending oils are used alone or in combination of two or more. Among these, the extending oil is preferably an aroma oil. Examples of the aroma oil include “Vivatec 500” manufactured by H & R.

  Although it does not specifically limit as addition amount of extending oil, It is preferable that it is 10-60 mass parts with respect to 100 mass parts of conjugated diene polymers, and it is more preferable that it is 15-45 mass parts.

(Carbon black E)
In the first kneading step, carbon black E is preferably further added and kneaded. Carbon black E may be further added and kneaded after the aging process described later. Thereby, it exists in the tendency which improves the reinforcement property of the conjugated diene type polymer composition obtained further. The carbon black E is not particularly limited, and for example, carbon black of each class such as SRF, FEF, HAF, ISAF, SAF, etc. can be used. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or more is preferable from the viewpoint of extrusion moldability and rolling resistance characteristics.

  The amount of carbon black E added is 0.5% with respect to 100 parts by mass of the conjugated diene polymer A from the viewpoint of further improving the rolling resistance characteristics due to the addition of the silica-based inorganic filler B and further improving the extrusion processability. -100 mass parts is preferable, 3-100 mass parts is more preferable, and 5-50 mass parts is further more preferable.

(Vulcanization aid)
From the viewpoint of promoting vulcanization molding in the first kneading step, it is preferable to further add a vulcanization aid and knead. Examples of the vulcanization aid include zinc white and / or stearic acid. The addition amount of the vulcanization aid is preferably 1 to 10 parts by mass and more preferably 2.5 to 6.5 parts by mass with respect to 100 parts by mass of the conjugated diene polymer A.

(Lubricant)
In the first kneading step, it is preferable to further add a lubricant and knead. This tends to further improve the processability and moldability of the resulting conjugated diene polymer composition. Examples of the lubricant include wax, and examples thereof include “Sannok” manufactured by Ouchi Shinsei Chemical Co., Ltd.

  The addition amount of the lubricant is preferably 1.0 to 2.0 parts by mass with respect to 100 parts by mass of the conjugated diene polymer A.

(Anti-aging agent)
In the first kneading step, it is preferable to further add an anti-aging agent and knead. As an antiaging agent, a well-known antiaging agent is mentioned, For example, N-isopropyl-N'-phenyl-p-phenylenediamine is mentioned.

  The addition amount of the antioxidant is preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the conjugated diene polymer.

(Metal oxide or metal hydroxide)
In the first kneading step, it is preferable to further add and knead a metal oxide or metal hydroxide. The metal oxide refers to solid particles having a chemical unit M _x O _y (M represents a metal atom, and x and y each represents an integer of 1 to 6) as a main component of a structural unit. Examples of the metal oxide include alumina, titanium oxide, magnesium oxide, and zinc oxide. The metal oxide may contain an inorganic filler other than the metal oxide (excluding the silica-based inorganic filler B) as a mixture. The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

  As for the addition amount of a metal oxide and a metal hydroxide, 1.0-5.0 mass parts is preferable with respect to 100 mass parts of conjugated diene polymers.

(Rubber softener)
In the first kneading step, from the viewpoint of further improving the workability, a rubber softener may be further added and kneaded. As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable.

  The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system. As the rubber softener used together with the modified conjugated diene-aromatic vinyl copolymer, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.

  0-100 mass parts is preferable with respect to 100 mass parts of rubber components A, as for the compounding quantity of the rubber softener, 10-90 mass parts is more preferable, and 30-90 mass parts is further more preferable.

  When the addition amount of the rubber softening agent is 100 parts by mass or less with respect to 100 parts by mass of the rubber component A, generation of bleed out can be further suppressed, and the surface of the conjugated diene polymer composition of the present embodiment becomes sticky. Can be prevented.

(Additive)
In the conjugated diene polymer composition of the present embodiment, other softeners and fillers, heat resistance stabilizers, antistatic agents, weather resistance stabilizers other than those described above, within the range not impairing the purpose of the present embodiment, Various additives such as colorants and tackifiers (coumaron-based, indene-based, petroleum-based resins, etc.) may be used. As other softeners, known softeners can be used. Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. As the above heat stabilizer, antistatic agent, weather stabilizer, and colorant, known materials can be used.

(Aging process)
In the aging process of the kneaded product obtained in the first kneading process, the aging temperature is 40 ° C. or higher. In the present specification, the “aging step” refers to holding the kneaded product obtained in the first kneading step for a certain period of time in an environment of a certain temperature range. The polymer composition may be held indoors or in an oven as long as the temperature can be kept constant to some extent. During the aging process, in general, nothing is done to the composition, but the polymer composition is gently stirred or given vibration at regular intervals as long as the shape after the operation does not change significantly. , "Aging" category. The shape of the composition during aging is not particularly limited. For example, the polymer composition can be stored in a sheet form after being processed into a sheet.

  When the aging temperature is 40 ° C. or higher, the wear resistance is improved without impairing rolling resistance characteristics and wet skid resistance. The aging temperature is more preferably 40 to 80 ° C., and even more preferably 50 to 80 ° C. from the viewpoints of workability and wear resistance. It is preferable to hold the kneaded material for about 20 to 150 hours after the center temperature of the kneaded material reaches 40 ° C. so that the kneaded material is uniformly aged to the center. By setting the upper limit of the temperature to 80 ° C., the kneaded product can suppress an increase in viscosity, which is preferable in that the workability of the second kneading step can be maintained well. The environmental temperature during the aging step may be limited as long as it is within a preferable temperature range, but the change in the environmental temperature is generally 80 ° C. or lower, preferably 40 to 80 ° C. In addition, the aging time is not particularly limited, but it is preferable to set it to, for example, one day or more from the viewpoint of uniformly aging the composition to the center. On the other hand, the upper limit of the period is preferably 7 days or less from the viewpoint of suppressing deterioration of workability due to excessive progress of filler re-aggregation.

  In the manufacturing method of the present embodiment, the aging process is performed between the first kneading process and the second kneading process in which the vulcanizing agent D is further added and kneaded. Here, between the aging step and the second kneading step, the step of re-kneading the kneaded product obtained in the aging step without blending (adding) anything, Component A, Component B Alternatively, a part of component C and the above-mentioned other components may be added (blended) collectively or sequentially and kneaded. When there are a plurality of kneading steps, aging may be performed before the second kneading step in which the vulcanizing agent D is further added and kneaded, and even after aging after the first kneading, Aging may be carried out after the second stage of kneading, but it is preferable to age after the second stage of kneading from the viewpoint of wear resistance. Aging may be performed both after the first stage kneading and after the second stage kneading from the viewpoint of the performance of the conjugated diene polymer composition, but from the viewpoint of production efficiency, It is preferable to perform an aging process after kneading one of them.

(Second kneading step)
The kneading temperature in the second kneading step is not particularly limited. For example, 105 ° C. or lower is preferable from the viewpoint of suppressing the vulcanization reaction in this step, and 70 ° C. or higher is preferable from the viewpoint of workability.

  In the second kneading step, a vulcanization accelerator may be further added and kneaded. As the vulcanization accelerator, conventionally known materials can be used as the vulcanization accelerator. For example, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiol-based, Examples of the vulcanization accelerator include urea and dithiocarbamate. The usage-amount of a vulcanization accelerator is 0.01-20 mass parts normally with respect to 100 mass parts of rubber component A containing a modified conjugated diene polymer, and 0.1-15 mass parts is preferable.

  In the production method of the modified conjugated diene polymer composition of the present embodiment, as a method of kneading various materials, a conventionally known method can be applied and is not limited to the following, but for example, open A melt kneading method using a general blender such as a roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., and after dissolving and mixing the components, the solvent is removed by heating. Methods and the like.

  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 various materials at a time and a method of kneading in a plurality of times can be applied.

  The conjugated diene polymer composition of the present embodiment is suitable for treads, and is suitable for tire applications including a tread containing a crosslinked product of the conjugated diene polymer of the present embodiment.

  That is, a tire can be manufactured by manufacturing a tread using the conjugated diene polymer composition of this embodiment, bonding together with other members, and heating and pressing using a tire molding machine.

  By using the conjugated diene polymer composition of the present embodiment, it is possible to produce a tire with high wear resistance without impairing rolling resistance characteristics and wet skid resistance. For this reason, the manufacturing method of a tire including the process of obtaining a tread using the crosslinked material of the conjugated diene polymer composition of this embodiment is also included in the present invention.

  Hereinafter, the present embodiment will be described in more detail with specific examples and comparative examples. However, the present embodiment is not limited to the following examples.

[Production Example 1]
An autoclave having an internal volume of 5 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were previously removed. 265 g of 1,3-butadiene, 93 g of styrene, 2030 g of cyclohexane, 2,2 as a polar substance -3.8 mmol of bis (2-oxolanyl) propane was put into the reactor, and the temperature inside the reactor was kept at 50 ° C. As a polymerization initiator, a cyclohexane solution of 1-lithiopiperidine (5.10 mmol) obtained by reacting piperidine (5.10 mmol) and n-butyllithium (5.10 mmol) was supplied to the reactor. After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the exotherm caused by the polymerization, and the final temperature inside the reactor reached 78 ° C.

  Two minutes after reaching the peak of the reaction temperature, 0.587 mmol of tris (3-trimethoxysilylpropyl) amine was added to the reactor, and a denaturation reaction was carried out for 5 minutes.

  After adding 1.0 g of an antioxidant (2,6-di-tert-butyl-4-hydroxytoluene; BHT) to this polymer solution, the solvent is removed by steam stripping, and drying treatment is performed by a dryer. The conjugated diene polymer 3 having a molecular structure branched from the nitrogen-containing alkoxysilane substituent was obtained.

[Production Example 2]
Using an autoclave with an internal volume of 5 L (L / D: 3.4) and a temperature-controllable autoclave equipped with a stirrer and a jacket, it may interfere with the polymerization reaction existing in the reactor with 1995 g of normal hexane. For neutralization of impurities, n-butyllithium was put into the reactor, stirred at 70 ° C. for 5 minutes, cooled to room temperature, the solution was taken out, and the reactor was emptied.

  Next, 1670 g of normal hexane from which impurities were previously removed, 83 g of styrene, 236 g of 1,3-butadiene, and 3.50 mmol of 2,2-bis (2-oxolanyl) propane as a polar substance were placed in the reactor. Was 50 ° C., 3.59 mmol of n-butyllithium was added as a polymerization initiator to initiate polymerization.

  Immediately after the start of polymerization, the temperature in the reactor increased and reached a peak temperature, which was 81 ° C. When a decrease in temperature was confirmed, 0.38 mmol of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine adjusted to 50 ° C. was added as a coupling agent, and the mixture was further stirred for 10 minutes. The stirring speed at this time is 200 rpm. Met. The coupling agent was added 2 minutes after the peak temperature was reached.

  2.92 mmol of ethanol was added as a polymerization terminator to stop the reaction, and a modified conjugated diene polymer-containing polymer solution was obtained.

  To the resulting polymerization solution, 0.64 g of 2,6-di-tert-butyl-4-hydroxytoluene as an antioxidant and 4 “Vivatec 500” manufactured by H & R as extension oil for 100 g of the polymer were added. .3 g (4.3 parts by mass), and after mixing with a mixer, the solvent is removed by steam stripping, and after vacuum drying, the molecular structure branched from the nitrogen-containing alkoxysilane substituent is obtained. A conjugated diene copolymer 4 was obtained.

[Production Example 3]
An autoclave having an internal volume of 10 L and a stirrer and a jacket was used as a reactor, and cyclohexane and normal butyl lithium were added to the reactor and washed, followed by nitrogen substitution, 4583 g of cyclohexane, 47.4 g of divinylbenzene, 1 1,3 butadiene was added and the temperature in the reactor was maintained at 40 ° C., and then 341 g of n-butyllithium solution was added and reacted for 90 minutes to raise the temperature in the reactor to 80 ° C. Thereafter, the mixture was allowed to cool in the reactor for 2 hours to prepare a polyfunctional catalyst.

  The n-butyllithium solution of the raw material was a solution having a weight mixing ratio of n-butyllithium / cyclohexane of 20/80. The divinylbenzene contained m-divinylbenzene, p-divinylbenzene, ethylbenzene and the like, and a divinylbenzene mixture (manufactured by Nippon Steel Chemical Co., Ltd.) having a divinylbenzene concentration of 57% by mass was used.

  Using an autoclave having an internal volume of 40 L and a jacket as a reactor, cyclohexane and normal butyl lithium were added to the reactor and washed, and then nitrogen substitution was performed. In the reactor, 20915 g of cyclohexane, 779 g of styrene, After adding 4.5 g of 2,2-bis (2-oxolanyl) propane and 2221 g of butadiene as polar compounds and maintaining the temperature in the reactor at 45 ° C., 204 g of polyfunctional anion initiator was added and the polymerization reaction was started. The peak temperature in the reactor reached 83 ° C. and the polymerization reaction was completed. One minute after the completion of the polymerization reaction, 5.6 g of 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine as a modifier was fed into the reactor at an addition rate of 5 seconds or less. After the modification reaction, the solvent was removed by steam stripping, and vacuum drying was performed to obtain a conjugated diene polymer 5 having a molecular structure branched from a nitrogen-containing alkoxysilane substituent. As the n-butyllithium solution, a solution having a weight mixing ratio of 20/80 of n-butyllithium / cyclohexane was used.

  In Examples and Comparative Examples, the physical properties of the polymers were measured by the methods shown below.

(Physical property 1) Rolling resistance characteristic The viscoelasticity parameter was measured by the torsion mode using the viscoelasticity testing machine (ARES-G2) by TA Instruments.
The measured values of Example 1 and Comparative Example 1 were indexed with Comparative Example 1 as 100. The measured values of Examples 2 to 5 and Comparative Examples 2 to 4 were indexed as Comparative Example 2100.
Tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of rolling resistance characteristics (low fuel consumption). Each measured value was indexed with Comparative Example 1 as 100 for each Example and Comparative Example. A smaller value indicates better rolling resistance characteristics.

(Physical property 2) Wet skid resistance Viscoelastic parameters were measured in a torsion mode using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments.
Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet skid resistance (wet brake performance).
The measured values of Example 1 and Comparative Example 1 were indexed with Comparative Example 1 as 100. The measured values of Examples 2 to 5 and Comparative Examples 2 to 4 were indexed with Comparative Example 2 as 100. It shows that wet skid resistance is so favorable that a value is large.

(Physical property 3) Abrasion resistance Using an Akron abrasion tester (manufactured by Yasuda Seiki Seisakusho), according to JIS K6264-2, the wear amount of load 44.1N, 3000 rotations was measured and evaluated based on the following criteria. .
The measured values of Example 1 and Comparative Example 1 were indexed with Comparative Example 1 as 100. The measured values of Examples 2 to 5 and Comparative Examples 2 to 4 were indexed with Comparative Example 2 as 100. It shows that it is excellent in abrasion resistance, so that a value is small.

[Examples 1 to 14 and Comparative Examples 1 to 10]
The materials shown below were kneaded by the following method to produce an unvulcanized rubber composition and a vulcanized rubber composition.
Conjugated diene polymer 1: non-modified SBR (manufactured by Asahi Kasei Corporation, T2000, 0 parts by mass of extended oil in 100 parts by mass in total)
Conjugated diene polymer 2: Modified SBR (Asahi Kasei Co., Ltd., F3420, blending 25 parts by weight of extended oil in 125 parts by weight)
Conjugated diene polymer 3: Conjugated diene polymer produced in [Production Example 1] Conjugated diene polymer 4: Conjugated diene polymer produced in [Production Example 2] Conjugated diene polymer 5: Conjugated diene polymer / silica produced in [Production Example 3] (Evonik Japan Co., Ltd., Ultrasil 7000GR, Nitrogen adsorption specific surface area: 175 m ² / g)
・ Silane coupling agent (Si75, manufactured by Evonik Japan)
・ Extension oil (Hiva R, Vivatec 500)
・ Carbon black (Tokai Carbon Co., Ltd., Seast KH (N339))
・ Zinc flower (Mitsui Metal Mining Co., Ltd., Zinc flower No. 1)
・ Stearic acid and wax: (Onouchi Shinsei Chemical Co., Ltd., Sunnock)
・ Anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine)
・ Sulfur / vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide)
・ Vulcanization accelerator 2 (diphenylguanidine)

[Example 1]
According to the formulation shown in Table 1, kneading was performed by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet.
Using a kneader (with an internal volume of 0.5 L) equipped with a temperature control device, the conjugated diene polymer 1 (manufactured by Asahi Kasei Co., Ltd.) under the conditions of a filling rate of 65% and a rotor rotational speed of 50 rpm as the first stage kneading T2000) Using 100 parts by mass, silica, and a silane coupling agent, and with respect to 100 parts by mass of the conjugated diene polymer 1, the extension oil (V & C 500, manufactured by H & R Co., Ltd.) so that the total of the extension oil is 30 parts by mass. 30 parts by mass was blended and kneaded for 4 minutes. Subsequently, carbon black, zinc white, stearic acid, wax, and anti-aging agent were added and kneaded for 2 minutes. At this time, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader to obtain a blend.
Next, as the aging step, the kneaded product obtained above was aged in an oven at 80 ° C. for 7 days.
Further, as the second stage kneading, the compound obtained in the aging process was cooled to room temperature and then kneaded for 3.5 minutes without adding anything. Also in this case, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader. The discharge temperature was controlled by measuring the temperature of each formulation discharged from the kneader after kneading.
Furthermore, after cooling the composition obtained in the aging process to room temperature, the composition was heated using an oven at 80 ° C. for 30 minutes, and then kneaded at a temperature of 70 ° C. for 30 seconds as a third stage of kneading. After kneading, sulfur and a vulcanization accelerator were added and kneaded for 1.5 minutes and discharged at 105 ° C. to obtain a conjugated diene polymer composition (unvulcanized rubber composition).
Thereafter, vulcanization molding was performed with a vulcanization press at 160 ° C. for 20 minutes to obtain a vulcanized rubber sheet.
The rolling resistance characteristics, wet skid resistance characteristics, and wear resistance of the vulcanized rubber sheet were evaluated.

[Example 2]
As the conjugated diene polymer, 125 parts by mass of “conjugated diene polymer 2 (F3420 manufactured by Asahi Kasei Co., Ltd.)” was used instead of “conjugated diene polymer 1” (“conjugated diene polymer 2”). ”Contains 25 parts by weight of extender oil), and 15 parts by weight of extender oil is added so that the blended oil amount is 40 parts by weight including the extender oil in“ conjugated diene polymer 2 ”. Except for this, a vulcanized rubber molding was obtained in the same manner as in Example 1. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 3
In Example 2, instead of performing the aging step after the first kneading step, a vulcanized rubber molding was obtained in the same manner as in Example 2 except that the aging step was performed after the second kneading step. It was. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 4
In the aging process, a vulcanized rubber molded product was obtained in the same manner as in Example 3 except that the aging temperature was 40 ° C. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 5
In the aging step, a vulcanized rubber molded product was obtained in the same manner as in Example 3 except that the aging temperature was 50 ° C. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 6
As the conjugated diene polymer, 100 parts by mass of “conjugated diene polymer 3 (conjugated diene polymer produced in Production Example 1)” instead of “conjugated diene polymer 1” was used, and the aging step was performed. A vulcanized rubber molded product was obtained in the same manner as in Example 1 except that it was performed after the second kneading step instead of being performed after the first kneading step. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 7
Example except that 100 parts by mass of “conjugated diene polymer 4 (conjugated diene polymer produced in Production Example 2)” instead of “conjugated diene polymer 3” was used as the conjugated diene polymer. In the same manner as in No. 6, a vulcanized rubber sheet was obtained. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 8
Example except that 100 parts by mass of “conjugated diene polymer 5 (conjugated diene polymer produced in Production Example 3)” instead of “conjugated diene polymer 3” was used as the conjugated diene polymer. In the same manner as in No. 6, a vulcanized rubber molding was obtained. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 9
In Example 3, a vulcanized rubber molding was obtained in the same manner as in Example 3 except that the aging days were set to 1 day. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 10
In Example 3, a vulcanized rubber molding was obtained in the same manner as in Example 3 except that the aging days were changed to 4 days. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 11
In Example 3, the aging process was performed at an aging temperature of 80 ° C. and an aging day of 3 days after the first kneading process, and the aging process was further performed at an aging temperature of 80 ° C. and an aging day of 4 days after the second process. A vulcanized rubber molding was obtained in the same manner as in Example 3 except that the procedure was performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 12
A vulcanized rubber molding was obtained in the same manner as in Example 3 except that carbon black was not used. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 13
A vulcanized rubber molding was obtained in the same manner as in Example 3 except that 45 parts by mass of silica and 3.6 parts by mass of the silane coupling agent were used. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

Example 14
A vulcanized rubber molding was obtained in the same manner as in Example 3 except that 105 parts by mass of silica and 8.4 parts by mass of the silane coupling agent were used. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 1]
A vulcanized rubber molding was obtained in the same manner as in Example 1 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 2]
A vulcanized rubber molding was obtained in the same manner as in Example 2 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 3]
A vulcanized rubber molding was obtained in the same manner as in Example 2 except that the aging step was performed after vulcanization molding instead of being performed after the second kneading step. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 4]
A vulcanized rubber was obtained in the same manner as in Example 2 except that the aging temperature was 23 ° C. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 5]
A vulcanized rubber molding was obtained in the same manner as in Example 6 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 6]
A vulcanized rubber molding was obtained in the same manner as in Example 7 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 7]
A vulcanized rubber was obtained in the same manner as in Example 8 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 8]
A vulcanized rubber molding was obtained in the same manner as in Example 12 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

[Comparative Example 9]
A vulcanized rubber molding was obtained in the same manner as in Example 13 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.
[Comparative Example 10]
A vulcanized rubber molding was obtained in the same manner as in Example 14 except that the aging process was not performed. The rolling resistance characteristics, wet skid resistance, and wear resistance of the vulcanized rubber molding were evaluated.

  The compounding compositions of Examples 1 to 14 and Comparative Examples 1 to 10 are shown in Tables 1 and 2, and the rolling resistance characteristics and steering stability evaluation results are shown in Tables 3 to 10.

  From Tables 3-10, it turned out that the rubber composition of this invention is highly excellent in abrasion resistance, without impairing rolling resistance characteristics and wet skid resistance.

  On the other hand, it turned out that what is less than the manufacturing method of this invention like Comparative Examples 1-10 is inferior to the balance of rolling resistance characteristics, wet skid resistance, and abrasion resistance.

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

Claims (5)

A first kneading step of kneading the rubber component A containing the conjugated diene polymer, the silica-based inorganic filler B, and the silane coupling agent C;
An aging step of aging the kneaded product obtained by the first kneading step at a temperature of 40 ° C. or higher;
A method for producing a conjugated diene polymer composition, comprising: a kneaded product obtained in the aging step; and a second kneading step of kneading the vulcanizing agent D.   The production method according to claim 1, wherein carbon black E is added and further kneaded before and / or after the aging step.   A conjugated diene polymer composition produced by the production method according to claim 1.   The conjugated diene polymer composition according to claim 3, which is used for a tread.   A tire provided with a tread containing a cross-linked product of the conjugated diene polymer composition according to claim 3.