JP5127521B2 - Modified conjugated diene polymer, method for producing the same, and polymer composition - Google Patents

Description

  The present invention relates to a modified conjugated diene polymer and a method for producing the same. More specifically, the compound (A) having two or more epoxy groups is reacted with the active terminal of the conjugated diene polymer, and further a compound having a primary or secondary amino group and one or more alkoxysilyl groups (B And a polymer composition containing the resulting modified conjugated diene polymer and an inorganic filler.

In recent years, demands for reducing fuel consumption for automobiles have increased due to social demands such as the suppression of carbon dioxide emissions, and materials with lower rolling resistance have been demanded for automobile tires, particularly tire treads in contact with the ground. At the same time, from the viewpoint of safety, a tire excellent in wet skid resistance, wear resistance and fracture characteristics is desired.
In order to reduce the rolling resistance of the tire, it is only necessary to reduce the hysteresis loss of the vulcanized rubber, and natural rubber, polyisoprene rubber, polybutadiene rubber or the like is known as a rubber material having a small hysteresis loss. However, these have a problem of low wet skid resistance. As a method of reducing hysteresis loss without impairing wet skid resistance, reinforcing groups are introduced by introducing modified groups at the polymer ends of various structures of styrene-butadiene copolymers polymerized with organolithium initiators in hydrocarbon solvents. Many methods have been proposed to increase the interaction with the filler and increase the dispersibility of the filler. Examples of reinforcing fillers that are generally used for tire treads include carbon black and silica. The use of silica improves low hysteresis loss and wet skid resistance, and its use has increased in recent years. However, carbon black is often used in combination with dry skid resistance and running performance. The modified rubber is required to be effective for both silica and carbon black. For example, a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer terminal is preferably used ( (See Patent Documents 1 and 2). However, with the increasing demand for low fuel consumption, there has been a demand for a modified rubber having a higher interaction with the reinforcing filler.

On the other hand, it is known that a modified polymer having a primary amino group and an alkoxysilyl group at the polymer end group has an excellent effect in the interaction with the reinforcing filler. A step to remove the protecting group is required, and further, a protective residue such as trialkylsilanol is generated during deprotection and mixed into the solvent after desolvation, which adversely affects the polymerization step when reused as a polymerization solvent, etc. (Refer to patent document 3).
International Publication No. 87/05610 Pamphlet International Publication No. 01/23467 Pamphlet JP 2003-171418 A

  The present invention, when used as a tire tread material, obtains a tire tread having an excellent balance of wet skid characteristics, low hysteresis loss, wear resistance, and breaking strength regardless of the type and combination of fillers to be blended. It is an object of the present invention to provide a modified conjugated diene polymer, a production method thereof, and a composition thereof.

As a result of intensive studies and studies to solve the above-mentioned problems, the inventors of the present invention are excellent in using inorganic fillers such as silica and carbon black by modifying the active terminal of the polymer in two steps using a specific compound. Found that a modified conjugated diene polymer excellent in the balance of wet skid characteristics, low hysteresis loss, wear resistance, and fracture strength can be obtained when used as a tire tread material. It came to make this invention.
That is, in the present invention, the compound (A) having two or more epoxy groups is reacted at the active terminal of the conjugated diene polymer, and further, the primary or 2 with respect to all or part of the remaining epoxy groups. A method for producing a modified conjugated diene polymer characterized by reacting a compound (B) having a secondary amino group and one or more alkoxysilyl groups, a modified conjugated diene polymer obtained, and a composition thereof.

Details are as follows.
1. After (co) polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as an initiator, the active terminal is represented by the general formula (1) compounds having two or more epoxy groups (a) are reacted, to all or a portion of the epoxy groups are further remaining 3 having a primary or secondary amino groups and one or more alkoxysilyl group A modified conjugate characterized by reacting a compound (B) selected from -aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and (3-trimethoxysilylpropyl) diethylenetriamine A method for producing a diene polymer.

(Wherein R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms having an ether and / or a tertiary amine, R ³ and R ⁴ are hydrogen, 1 carbon atom, -20 hydrocarbon group, or ether and / or hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, or ether, tertiary amine, epoxy, carbonyl And a hydrocarbon group having 1 to 20 carbon atoms having at least one group out of halogen, and n is an integer of 1 to 6.)

2. The compound (A) having two or more epoxy groups represented by the general formula (1) at the terminal of the conjugated diene compound or the (co) polymer composed of the conjugated diene compound and the aromatic vinyl compound is at least one epoxy. 3-aminopropyl having a primary or secondary amino group and one or more alkoxysilyl groups bonded to all or part of the other epoxy group of the compound (A) by bonding of the group by ring opening Mooney, wherein compound (B) selected from triethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine is bonded by ring opening of an epoxy group A modified conjugated diene polymer having a viscosity (100 ° C., 1 + 4 minutes) of 20 to 100.
(Where R1 and R2 are hydrocarbon groups having 1 to 10 carbon atoms or ether and / or hydrocarbon groups having a tertiary amine, and R3 and R4 are hydrogen, carbon atoms having 1 to 20 carbon atoms. A hydrogen group, or a hydrocarbon group having 1 to 20 carbon atoms having an ether and / or a tertiary amine, R5 is a hydrocarbon group having 1 to 20 carbon atoms, or at least one of ether, tertiary amine, epoxy, carbonyl, and halogen. (It is a C1-C20 hydrocarbon group which has 1 type of group, and n is an integer of 1-6.)
3. 2. A modified conjugated diene polymer composition comprising 100 parts by mass of the polymer containing the modified conjugated diene polymer according to 1) and 1 to 200 parts by mass of a filler.
4). 2. The filler containing carbon black and / or silica . The modified conjugated diene polymer composition described in 1.

  The modified conjugated diene polymer obtained in the present invention is excellent in affinity with an inorganic filler, and when used as a tire tread material, the wet skid property, low A tire tread having a good balance of hysteresis loss, wear resistance, and breaking strength can be obtained.

The present invention will be specifically described below.
As the alkali metal initiator or alkaline earth metal initiator used in the production method of the present invention, any alkali metal initiator or alkaline earth metal initiator capable of initiating polymerization can be used. Among these, at least one compound selected from the group consisting of organic alkali metal compounds and organic alkaline earth metal compounds is preferably used.
As the organic alkali metal compound, an organic lithium compound is particularly suitable. Organic lithium compounds having a low molecular weight, solubilized oligomeric organic lithium compounds, those having a single lithium in one molecule, those having a plurality of lithiums in one molecule, and bonding of an organic group and lithium In the form, those comprising a carbon-lithium bond, those comprising a nitrogen-lithium bond, those comprising a tin-lithium bond, and the like are included.

  Specifically, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenelithium and the like as monoorganolithium compounds are 1,4 as polyfunctional organolithium compounds. -Dilithiobutane, sec-butyllithium and diisopropenylbenzene reaction product, 1,3,5-trilithiobenzene, n-butyllithium, 1,3-butadiene and divinylbenzene reaction product, n-butyllithium and polyacetylene compound In addition, as a compound having a nitrogen-lithium bond, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethylene Bromide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium morpholinocarbonyl soil. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to. Particularly preferred are n-butyllithium and sec-butyllithium. These organolithium compounds may be used as a mixture of not only one but also two or more.

Examples of other organic alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, lithium, sodium, potassium alkoxides, sulfonates, carbonates, amides, and the like are used. Moreover, you may use together with another organometallic compound.
On the other hand, examples of the alkaline earth metal compound include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Specific examples include dibutyl magnesium, ethyl butyl magnesium, and propyl butyl magnesium. In addition, alkaline earth metal compounds such as alkoxides, sulfonates, carbonates, and amides are used. These organic alkaline earth metal compounds may be used in combination with organic alkali metal initiators and other organic metal compounds.

In the present invention, the conjugated diene polymer is preferably obtained by polymerizing with the alkali metal initiator and / or alkaline earth metal initiator described above and growing by an anionic polymerization reaction, particularly by living anionic polymerization. A polymer having an active end obtained by a growth reaction is preferred. As a production method, the polymerization can be carried out by a polymerization system such as a batch system or a continuous system in one reactor or two or more connected reactors.
The conjugated diene polymer is a polymer or copolymer of a conjugated diene compound, and further a copolymer of a conjugated diene compound-aromatic vinyl compound. In the polymerization reaction of conjugated diene polymers, for the purpose of random copolymerization of aromatic vinyl compounds with conjugated diene compounds, as a vinylating agent for controlling the microstructure of the conjugated diene part, and further to improve the polymerization rate It is also possible to add a small amount of a polar compound for the purpose.

  Polar compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl) propane, tetra Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine, etc., potassium tert-amylate, potassium tertbutylate, sodium tertbutylate, sodium amylate, etc. A phosphine compound such as an alkali metal alkoxide compound or triphenylphosphine is used. These polar compounds can be used alone or in combination of two or more.

The amount of the polar compound used is selected according to the purpose and the degree of effect. Usually, 0.01-100 mol is preferable with respect to 1 mol of initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount depending on the desired vinyl bond amount as a microstructure modifier for the polymer diene moiety. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. The randomizing method may be a method of intermittently adding a part of 1.3-butadiene during the copolymerization as described in JP-A-59-140221.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene etc. are mentioned, You may use 1 type or in combination of 2 or more types. Preferred compounds include 1,3-butadiene and isoprene. Examples of the aromatic vinyl compound include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and the like, and one or a combination of two or more may be used. good. A preferred compound is styrene.

The polymerization temperature is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, the polymerization temperature is 0 ° C. or higher, and the viewpoint of sufficiently securing the reaction of the compound (A) to the active terminal after the polymerization is completed. The polymerization is preferably carried out at a temperature of 120 to 120 ° C.
In order to prevent cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene can be used from the viewpoint of controlling branching.
The molecular weight (weight average molecular weight: in terms of polystyrene) of the conjugated diene polymer produced is preferably 100,000 to 2,000,000 in view of processability and physical properties.
The weight average molecular weight is measured, for example, by measuring the chromatogram using GPC using three columns connected with polystyrene gel as a filler, and calculating the molecular weight with a calibration curve using standard polystyrene. Can be obtained. Specifically, tetrahydrofuran (THF) is used as an eluent, guard columns: Tosoh TSKguardcolumn HHR-H, columns: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR are used as the column, oven temperature 40 ° C., THF flow rate Measurement can be performed using Tosoh HLC8020 (detector: RI) under the conditions of 1.0 ml / min. It is preferable to measure 10 mg in the case of a polymer having a narrow molecular weight distribution in 20 ml of THF and 20 mg in the case of a wide polymer, and inject 200 μl of the sample.

  Examples of the hydrocarbon solvent used in the method for producing a conjugated diene polymer include saturated hydrocarbons and aromatic hydrocarbons, and aliphatic hydrocarbons such as butane, pentane, hexane, pentane and heptane, cyclopentane and cyclohexane. Hydrocarbons such as alicyclic hydrocarbons such as methylcyclopentane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and mixtures thereof can be used. In conjugated diene compounds, aromatic vinyl compounds, and hydrocarbon solvents, treatment of allenes and acetylenes, which are impurities, with an organometallic compound before the polymerization reaction of each or each mixed solution is carried out at a high concentration It is preferable because a polymer having an active terminal can be obtained and a high modification rate can be achieved.

In order for the excellent effect of the present invention to be particularly exerted, a polymer containing a functional group component is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more. It is preferable to produce a conjugated diene polymer. As a method for quantifying a polymer having a functional group component, it can be measured by chromatography capable of separating a functional group-containing modified component and a non-modified component. As the chromatography method, a GPC column using a polar substance such as silica adsorbing a functional group component as a packing material and using an internal standard of the non-adsorbed component for comparison is suitable.
Examples of the conjugated diene polymer include a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer. . Examples of the random copolymer include a completely random copolymer having a statistically random composition, and a tapered random copolymer having a tapered distribution in composition. Even if it is a homopolymer of a single monomer composition, it is a polymer with a uniform composition due to its monomer bonding mode, that is, 1,4 bond and 1,2 bond, etc. (With block bonds) and various structures are possible.

  Examples of block bonds include those in which homopolymer blocks are bonded, blocks in which random polymers are bonded, and blocks in which tapered random polymers are bonded. Further, there are 2 type block copolymers composed of 2 blocks, 3 type block copolymers composed of 3 blocks, 4 type block copolymers composed of 4 blocks, and the like. As an example of a block polymer, a block made of an aromatic vinyl compound such as styrene is S, and a block made of a conjugated diene compound such as butadiene or isoprene and / or a block made of a copolymer of an aromatic vinyl compound and a conjugated diene compound is used. When represented by B, there are an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, and the like.

More generally, examples of the block polymer include structures such as (SB) k, S- (BS) k, and B- (SB) k.
(In the above formula, the boundary of each block does not necessarily need to be clearly distinguished. 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 is uniformly distributed. The block B may be distributed in a tapered shape, and the block B may have a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or a portion where the aromatic vinyl compound is distributed in a tapered shape. A plurality of segments having different aromatic vinyl compound contents may coexist in the block B. k is an integer of 1 or more, preferably an integer of 1 to 5. .) The block polymer may be any mixture having the structure represented by the above general formula.

In the present invention, after the (co) polymerization of the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound, the compound (A) having two or more epoxy groups at the obtained active terminal is reacted. Let
Specific examples of the compound (A) include aromatic compounds having two or more phenyl groups such as polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, and diglycidylated bisphenol A. Polyglycidyl ether, 1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene, polyepoxy compounds such as polyepoxidized liquid polybutadiene, 4,4′-diglycidyl-diphenylmethylamine, 4,4′- Epoxy group-containing tertiary amine such as diglycidyl-dibenzylmethylamine, diglycidyl aniline, diglycidyl orthotoluidine, tetraglycidyl meta-xylene diamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-pheny It has epoxy groups and other functional groups such as diglycidylamino compounds such as diamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane, epoxy modified silicone, epoxidized soybean oil, epoxidized linseed oil, etc. Compounds. These compounds may be used alone or in combination of two or more. More preferred is a compound having a diglycidylamino group in the molecule represented by the general formula (1).

(Wherein R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms having an ether and / or a tertiary amine, R ³ and R ⁴ are hydrogen, 1 carbon atom, -20 hydrocarbon group, or ether and / or hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, or ether, tertiary amine, epoxy, carbonyl And a hydrocarbon group having 1 to 20 carbon atoms having at least one group out of halogen, and n is an integer of 1 to 6.)

Here, compounds in which n is 2 or 3 are particularly preferred, for example, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethyl And cyclohexane.
The compound (A) is added to such an extent that a part of the epoxy group remains after the reaction between the epoxy group in the compound and the active terminal of the conjugated diene polymer. The amount of compound (A) added is A mole, the number of epoxy groups of compound (A) is f (the number of mole average when two or more types are used), and the total amount of alkali (earth) metal added as an initiator is M. It is preferably added so that the A / M value is 1 / f or more and 1 or less, and more preferably 3 / 2f or more and 1 or less. In order to secure an epoxy group with which the compound (B) reacts in a later step, it is preferably 1 / f or more, and preferably 1 or less from the viewpoint of cost.
There is no restriction | limiting in particular in the temperature which adds a compound (A) to an active terminal, It can add by adding, without especially adding and removing heat after superposition | polymerization of a conjugated diene type polymer. The reaction time is not particularly limited, but it is preferable to secure a reaction time of 30 seconds or longer until the compound (B) is added in order to obtain a sufficient reaction rate.

In the present invention, a primary or secondary amino group with respect to all or part of the epoxy group remaining after adding the compound (A) having two or more epoxy groups to the conjugated diene polymer. And a compound (B) having one or more alkoxysilyl groups is reacted.
As the compound (B) having a primary or secondary amino group and one or more alkoxysilyl groups, aminoalkyltrialkoxysilane, aminoalkylalkyldialkoxysilane, aminoalkyldialkylalkoxysilane, N- (aminoalkyl) aminoalkyltri Alkoxysilane, N- (aminoalkyl) aminoalkylalkyldialkoxysilane, N- (aminoalkyl) aminoalkyldialkylalkoxysilane, (trialkoxysilylalkyl) dialkylenetriamine, (alkyldialkoxysilylalkyl) dialkylenetriamine, ( Dialkylalkoxysilylalkyl) dialkylenetriamine, N-alkylaminoalkyltrialkoxysilane, N-alkylaminoalkylalkyldialkoxysilane, -Alkylaminoalkyldialkylalkoxysilane, N-arylaminoalkyltrialkoxysilane, bis (trialkoxysilylalkyl) amine, bis (alkyldialkoxysilylalkyl) amine, bis (trialkoxysilylalkyl) ethylenediamine, N-[(tri Alkoxysisilyl) -alkyl] -piperazine, N-[(alkyldiethoxysilyl) -alkyl] -piperazine, N-[(trialkoxysilyl) -alkyl] -imidaziridine, N-[(alkyldialkoxysilyl) -alkyl ] -Imidaziridine, N-[(dialkylalkoxysilyl) -alkyl] -imidazolidine, N-[(trialkoxysilyl) -alkyl] -hexahydropyrimidine, N-[(alkyldialkoxysilyl)- Alkyl] - hexahydropyrimidine, N - [(dialkyl alkoxysilyl) - alkyl] - hexahydropyrimidine and the like, and specific examples thereof include the following compounds.

  3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, (aminoethylamino) -3-isobutyldimethylmethoxysilane, N- ( 6-aminohexyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, (aminoethylaminomethyl) phene Ethylenetri Toxisilane, (3-trimethoxysilylpropyl) diethylenetriamine, N-methylaminopropyltriethoxysilane, N-butylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N- Cyclohexylaminopropyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, bis (methyldiethoxysilylpropyl) amine, bis [(3-trimethoxysilyl) propyl]- Ethylenediamine, N- [3- (triethoxysilyl) -propyl] -piperazine, N- [3- (methyldiethoxysilyl) -propyl] -piperazine, N- [3- (dimethylmethoxysilyl) -pro Le - Imidajirijin, N- [3- (ethyl-dimethoxy silyl) - propyl] - a hexahydropyrimidine or the like. In particular, the use of a compound having a primary amino group is preferable because a secondary amino group is generated by reaction with an epoxy group and a better interaction with an inorganic filler, particularly carbon black, can be expected. Preferred compounds include 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine and the like.

  These compounds may be used alone or in combination of two or more, and all or part of the epoxy groups remaining after adding the compound (A) having two or more epoxy groups to the active terminal of the conjugated diene polymer. To react against. After adding the compound (A), the compound (B) may be mixed and reacted in the solution, or the compound (B) is mixed with the polymer obtained by removing the solvent once with an internal mixer or the like. However, it is preferable to react by adding and mixing the compound (B) to the modified conjugated diene polymer solution obtained by reacting the compound (A) from the viewpoint of reaction efficiency. . There are no particular restrictions on the reaction temperature, reaction time, etc., but the reaction is preferably carried out at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer.

  According to this method, the compound (A) having two or more epoxy groups at the terminal of a conjugated diene compound or a (co) polymer composed of a conjugated diene compound and an aromatic vinyl compound opens at least one epoxy group. The compound (B) which is bonded by a ring and further has a primary or secondary amino group and one or more alkoxysilyl groups with respect to all or part of other epoxy groups of the compound (A) is an epoxy group. A modified conjugated diene-based polymer bonded by ring-opening can be obtained. Further, the active terminal of the polymer has a functional group such as an alkoxysilyl group, amino group, epoxy group, hydroxyl group or the like within 50 carbon atoms, preferably within 30 carbon atoms, without crushing the alkoxysilyl group. A terminal-modified polymer existing in a narrow range can be obtained.

  For example, tetraglycidyl-1,3-bisaminomethylcyclohexane represented by the following formula with respect to the active terminal of the conjugated diene polymer:

As an example of the structure of the modified polymer obtained by reacting 3-aminopropyltriethoxysilane after reacting with the following structure, the following structure is conceivable.

(Here, D represents a conjugated diene polymer chain.) The actual modified conjugated diene polymer has a conjugated diene polymer chain having four epoxy groups of tetraglycidyl-1,3-bisaminomethylcyclohexane. It is obtained as a mixture in which 1 to 4 of them are bonded and 3-aminopropyltriethoxysilane is bonded to some or all of the remaining epoxy groups. The -OLi produced when the conjugated diene polymer is bonded is converted to -OH in the course of reaction with a reaction terminator such as alcohol or water or steam stripping. When the compound (B) has a primary amino group and the portion thereof reacts with an epoxy group, a modified structure having a secondary amino group and a hydroxyl group is formed, and has a secondary amino group and the portion When reacts with an epoxy group, a modified structure having a tertiary amino group and a hydroxyl group is formed.

In the method for producing a modified conjugated diene polymer, a reaction terminator can be added to the solution of the inert solvent of the polymer, if necessary. As the reaction terminator, alcohols such as methanol, ethanol and propanol, organic acids such as stearic acid, lauric acid and octanoic acid, and water are usually used. The reaction terminator can be added before or after the addition of compound (B).
Further, if necessary, the metals contained in the polymer can be deashed. Usually, deashing is carried out by bringing water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide into contact with the polymer solution to extract metals, and then separating the aqueous layer.

Moreover, an antioxidant can be added to the solution of the inert solvent of the polymer. Antioxidants include phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers and the like.
The method for obtaining the polymer from the polymer solution can be performed by a known method. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain a polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. A method, a method of directly devolatilizing with a drum dryer or the like can be adopted.
When a filler selected from the group consisting of silica, carbon black, metal oxide and metal hydroxide is dispersed in a conjugated diene polymer and a conjugated diene polymer composition having a modifying group, it is superior to the conventional one. An effect is obtained. Particularly preferred is a method using synthetic silicic acid having a primary particle diameter of 50 nm or less as silica. In this case, the filler is quickly and uniformly dispersed in a fine particle form by kneading in a short time with good reproducibility, and the physical properties obtained are extremely favorable.

In the present invention, the case of producing a conjugated diene random copolymer as one of preferred embodiments will be described in more detail.
A conjugated diene or a combination of conjugated diene and styrene is used as a monomer, and a living conjugated diene homopolymer or a conjugated diene and styrene living random copolymer is obtained in an inert solvent using an organic monolithium compound as an initiator. The polymer has a glass transition temperature in the range of −100 ° C. to 0 ° C., and the ratio of 1,4-bond to 1,2 or 3,4 bond in the conjugated diene part is 10/90 to 90/10. The amount of bound styrene in the copolymer is 0 to 50% by mass, and the chain distribution of styrene in the copolymer is more preferably a completely random structure. That is, the isolated styrene (one unit of styrene) by ozonolysis method is 40% by mass or more of the total bonded styrene, and the chain styrene (a series of 8 or more styrene) is 5% by mass of the total bonded styrene. % Or less, preferably 2.5% by mass or less. The content of a styrene single chain having one styrene unit and a styrene long chain having 8 or more styrene units connected is determined according to the method of Tanaka et al. (Polymer, 22, 1721 (1981)). And then analyzed by gel permeation chromatography (GPC). The compound (A) having two or more epoxy groups is added to the living polymer solution, and the mixture is stirred and mixed uniformly to react with the active terminal, and then the primary or secondary amino group and one or more alkoxysilyls. The group-containing compound (B) is added and mixed to react with all or part of the remaining epoxy group.

In another preferred embodiment, a conjugated diene block copolymer may be produced.
In general, the molecular weight of the polymer is controlled according to the application and purpose. The Mooney viscosity (100 ° C. 1 + 4 minutes) of the modified conjugated diene polymer of the present invention is controlled to 20-100. Preferably it is 40-90, More preferably, it is 45-80. When Mooney viscosity is high, considering the ease in the finishing process at the time of manufacture, it is usually an extender oil for improving the workability at the time of kneading, improving the dispersibility of the filler, and improving various physical properties by improving the dispersibility. Oil is extended to this range. As the extender oil, aroma oil, naphthenic oil, paraffin oil, and aroma substitute oil of 3% by mass or less of polycyclic aromatic compound (PCA) by the method of IP346 are preferably used. Examples of the aroma substitute oil include TDAE (Treated Displaced Aromatic Extracts) and MES (Middlely Extracted Solvate), such as Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), and MES (Middlely Extracted Solve). The amount of the extender oil used is arbitrary, but is usually 10 to 50 parts by mass with respect to 100 parts by mass of the polymer. Generally, 20 to 37.5 parts by mass are used.

When the polymer obtained by the production method of the present invention is used for vulcanized rubber applications such as tires, automobile parts such as anti-vibration rubber, and shoes, 1 to 200 parts by mass with respect to 100 parts by mass of the polymer. It is preferable to use a modified conjugated diene polymer composition containing the above filler. As fillers, silica, carbon black, calcium carbonate, talc, clay, aluminum hydroxide, magnesium hydroxide and other fillers, and short fiber fillers such as polyester fiber, aramid fiber, nylon fiber, glass fiber, carbon fiber, etc. Can be used. These fillers may be used alone or in combination. Among these, silica is preferably used, and synthetic silicic acid having a primary particle diameter of 50 nm or less is particularly suitable. As the synthetic silicic acid, wet silica and dry silica are preferably used, and wet silica is more preferably used.
As the filler, carbon black can be preferably used. Carbon black is not particularly limited, and for example, furnace black, acetylene black, thermal black, channel black, graphite, and the like can be used. Among these, furnace black is particularly preferable.

  The polymer and the polymer composition of the present invention are composed of 1 to 100 parts by mass of silica and 1 to 100 parts by mass of carbon black alone or in combination with 100 parts by mass of the polymer. It is preferable to use it. Furthermore, it is more preferable to use it as a composition in which 20 to 100 parts by mass of silica and 1 to 80 parts by mass of carbon black are used in combination with 100 parts by mass of the polymer. In that case, as an effect of the present invention, the dispersibility of silica is particularly good, and the performance of the vulcanized rubber is excellent. Specifically, when silica and carbon black are uniformly dispersed to obtain a vulcanized rubber, a rubber having a storage modulus with little strain dependency can be obtained. In tire tread applications, the balance between rolling resistance and wet skid resistance is improved and wear resistance is improved, and strength is improved. Tire rubber, anti-vibration rubber, footwear, etc. Moreover, it becomes a suitable composition.

  The polymer and polymer composition of the present invention can be used alone or in admixture with other rubber as required. When used in combination with other rubber, if the proportion of the polymer according to the present invention is too small, the effect of the modification of the present invention is not sufficiently exhibited, which is not preferable. Other rubbers include, for example, natural rubber, polyisoprene rubber, emulsion polymerization styrene-butadiene copolymer rubber, solution polymerization random SBR (bonded styrene 5 to 50% by mass, 1,2-vinyl bond amount 10 in butadiene bond unit portion). ˜80%), high trans SBR (1,4-trans bond content of butadiene bond unit portion 70 to 95%), low cis polybutadiene rubber, high cis polybutadiene rubber, high trans polybutadiene rubber (1,4 of butadiene bond unit portion) -Trans bond amount 70-95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, solution polymerization random styrene-butadiene-isoprene copolymer rubber, emulsion polymerization random styrene-butadiene-isoprene copolymer rubber, emulsion polymerization Styrene-acrylonitrile-butadiene copolymer If rubber, acrylonitrile - butadiene copolymer rubber, high vinyl SBR- low vinyl SBR block Kyogo rubber, and polystyrene - polybutadiene - block copolymer and the like, such as polystyrene block copolymer. These can be appropriately selected according to required characteristics.

When the polymer according to the present invention and other rubber are used as the rubber component, the ratio of each component is usually 10/90 to 95/5, preferably 20/80 to 90/10, more preferably, by weight. It is in the range of 30/70 to 80/20. Further, as the rubber compounding agent, for example, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, oil, and the like can be further used.
The vulcanizing agent is not particularly limited. For example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur, and sulfur halides such as sulfur monochloride and sulfur dichloride. And organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide. Among these, sulfur is preferable, and powder sulfur is particularly preferable.
The blending ratio of the vulcanizing agent is usually 0.1 to 15 parts by mass, preferably 0.3 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. .

Examples of the vulcanization accelerator include sulfenamide-based, thiourea-based, thiazole-based, dithiocarbamic acid-based, xanthogenic acid-based vulcanization accelerators, and the like. The blending ratio of the vulcanization accelerator is usually 0.1 to 15 parts by mass, preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. is there.
The vulcanization aid is not particularly limited, and for example, stearic acid or zinc oxide can be used.
As the oil, for example, aroma oil, naphthene oil, paraffin oil, silicone oil or the like is selected according to the application. The amount of extender oil used is usually in the range of 1 to 150 parts by weight, preferably 2 to 100 parts by weight, and more preferably 3 to 60 parts by weight per 100 parts by weight of the rubber component. When the amount of oil used is within this range, the filler dispersion effect, tensile strength, abrasion resistance, heat resistance, etc. are balanced to a high value.

In addition to the above components, the composition using the polymer of the present invention and the polymer composition as a rubber component is an amine-based or phenol-based anti-aging agent, an ozone deterioration preventing agent, a silane coupling agent, diethylene glycol, in accordance with conventional methods. And other necessary additives such as an activator, a processing aid, a tackifier, and a wax.
The composition using the polymer of the present invention and the polymer composition as a rubber component is produced by mixing the above components using a known rubber kneading machine such as a roll or a Banbury mixer.
The modified conjugated diene polymer of the present invention is obtained by the above-described method for producing a modified conjugated diene polymer. And since the polymer of this invention consists of this structure, it has the outstanding effect as mentioned above.

Hereinafter, the present invention will be described based on examples. However, the present invention is not limited by these. In addition, the analysis of the sample in an Example was performed by the method shown below.
(1) Amount of bound styrene A sample was used as a chloroform solution, and the amount of bound styrene (mass%) was measured by absorption at UV254 nm by the phenyl group of styrene (manufactured by Shimadzu Corporation: UV-2450).
(2) Microstructure of butadiene moiety (1,2-vinyl bond content)
The sample was a carbon disulfide solution, the infrared spectrum was measured in the range of 600 to 1000 cm ⁻¹ using a solution cell, and the microstructure of the butadiene portion was determined from the predetermined absorbance according to the formula of the Hampton method (JASCO ( Co., Ltd .: FT-IR230).
(3) Mooney Viscosity According to JIS K 6300, the viscosity after 4 minutes was measured at 100 ° C. and 1 minute of preheating.

(4) Modification rate Applying the property that the modified component adsorbs to a GPC column using silica gel as a filler, using a sample solution containing a sample and standard polystyrene with a molecular weight of 5000 (polystyrene does not adsorb to the column), GPC (Tosoh HLC-8020) and polystyrene gel column (guard column: Tosoh TSKguardcolumn HHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR, oven temperature 40 ° C., THF flow rate 1.0 ml / min), silica System column (guard column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PSM-60S, oven temperature 40 ° C., THF flow rate 0.5 ml / min) Both chromatograms of GPC (Tosoh CCP8020 series build-up type GPC system: AS-8020, SD-8022, CCPS, CO-8020, RI-8021) were measured using an RI detector, and the silica column was determined from the difference between them. The amount of adsorption was measured to determine the modification rate. A sample was dissolved in 10 mg in the case of a polymer having a narrow molecular weight distribution with respect to 20 ml of THF, and 20 mg in the case of a wide polymer together with 5 mg of standard polystyrene, and 200 μl was injected for measurement. Specifically, the peak area of the chromatogram using a polystyrene column is defined as 100, the peak area of the sample polystyrene area is P1, the peak area of standard polystyrene is P2, and the peak area of the chromatogram using a silica column is calculated. The modification rate (%) can be obtained by [1- (P2 × P3) / (P1 × P4)] × 100, where 100 is the whole, the sample peak area is P3, and the peak area of standard polystyrene is P4.

[Example 1]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave with a stirrer and jacket was used as a reactor, 77 g of butadiene from which impurities were removed, 273 g of styrene, 4800 g of cyclohexane, 2,2-bis (2- Oxolanyl) propane (0.81 g) was charged into the reactor, and the reactor internal temperature was maintained at 42 ° C. A cyclohexane solution containing 9.5 mmol of n-butyllithium as a polymerization initiator was supplied to the reactor. After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 73 ° C. After the completion of the polymerization reaction, 4.3 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to the reactor, and the mixture was stirred at 72 ° C. for 2 minutes to carry out a denaturing reaction. .3 mmol was added and a denaturation reaction was carried out at 71 ° C. for 5 minutes. After adding 2.1 g of an antioxidant (BHT) to this polymer solution, the solvent is removed by steam stripping and drying is performed with a dryer to obtain a styrene-butadiene copolymer (sample A) having a modifying component. It was. The recovered solvent contained no substances harmful to polymerization other than water.
As a result of analyzing Sample A, the amount of bound styrene was 26% by mass, the amount of bound butadiene was 74%, and the Mooney viscosity of the polymer was 75. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer is 56%, and was determined from GPC using a silica-based adsorption column. The modification rate was 79%.

[Example 2]
A styrene-butadiene copolymer (sample B) having a modifying component was obtained in the same manner as for obtaining sample A, except that the amount of 3-aminopropyltriethoxysilane added was 8.6 mmol.
As a result of analyzing Sample B, the amount of bound styrene was 26% by mass, the amount of bound butadiene was 74%, and the Mooney viscosity of the polymer was 77. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer is 56%, and was determined from GPC using a silica-based adsorption column. The modification rate was 81%.

[Comparative Example 1]
A styrene-butadiene copolymer (sample C) having a modifying component was obtained in the same manner as that for obtaining sample A except that 3-aminopropyltriethoxysilane was not added.
As a result of analyzing Sample C, the amount of bound styrene was 26% by mass, the amount of bound butadiene was 74%, and the Mooney viscosity of the polymer was 74. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer is 56%, and was determined from GPC using a silica-based adsorption column. The modification rate was 82%.

[Comparative Example 2]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave with a stirrer and jacket was used as a reactor, 77 g of butadiene from which impurities were removed, 273 g of styrene, 4800 g of cyclohexane, 2,2-bis (2- Oxolanyl) propane (0.59 g) was charged into the reactor, and the reactor internal temperature was maintained at 43 ° C. A cyclohexane solution containing 7.1 mmol of n-butyllithium as a polymerization initiator was supplied to the reactor. After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 73 ° C. After completion of the polymerization reaction, 7.1 mmol of N-methyl-2-pyrrolidone was added to the reactor, and a denaturation reaction was performed at 72 ° C. for 5 minutes. After adding 2.1 g of an antioxidant (BHT) to this polymer solution, the solvent was removed to obtain a styrene-butadiene copolymer (sample D) having a modifying component.
As a result of analyzing Sample D, the amount of bound styrene was 26% by mass, the amount of bound butadiene was 74%, and the Mooney viscosity of the polymer was 52. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 57%, and was determined from GPC using a silica-based adsorption column. The modification rate was 83%.
The above preparation results are shown in Table 1.

[Examples 3 and 4 and Comparative Examples 3 and 4]
Using the samples shown in Table 1 (sample A to sample D) as raw rubber, a rubber composition was obtained with the following composition.
Modified conjugated diene-based polymer 70.0 parts by mass Polybutadiene rubber (UBEPOL-150) 30.0 parts by mass Silica (Ultrasil VN3 manufactured by Degussa) 75.0 parts by mass Carbon black (N339) 5.0 parts by mass Silane coupling agent (Degussa Si69) 7.5 parts by mass S-RAE oil (Japan Energy JOMO process NC140) 37.5 parts by mass zinc white 2.5 parts by mass stearic acid 2.0 parts by mass anti-aging agent (N-isopropyl -N'-phenyl-p-phenylenediamine) 2.0 parts by mass sulfur 1.7 parts by mass vulcanization accelerator (N-cyclohexyl-2-benzothiazylsulfinamide) 1.7 parts by mass vulcanization accelerator (diphenyl) Guanidine) 1.5 parts by mass total 236.4 parts by mass

The kneading method was performed as follows.
Using a closed kneader (with an internal volume of 0.3 liter) with a temperature controller, as the first stage of kneading, under the conditions of a filling rate of 65% and a rotor rotation speed of 50/57 rpm, raw rubber, filler (silica) And carbon black), organosilane coupling agent, process oil, zinc white, and stearic acid. At this time, the temperature of the closed mixer was controlled, and the rubber composition was obtained at a discharge temperature (compound) of 155 to 160 ° C.
Next, as the second stage kneading, the mixture obtained above was cooled to room temperature, an anti-aging agent was added, and kneaded again to improve the dispersion of silica. Also in this case, the discharge temperature (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
After cooling, as a third stage kneading, sulfur and a vulcanization accelerator were kneaded with an open roll set at 70 ° C.
This was molded, vulcanized with a vulcanizing press at 160 ° C. for 20 minutes, and the physical properties were measured. The physical property measurement results are shown in Table 2.

The measuring method of each physical property was implemented with the following method.
1) Bound rubber amount: About 0.2 gram of the blend after completion of the second stage kneading is cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight is measured. After soaking in toluene for 24 hours, dry, weigh, take into account undissolved components, calculate the amount of rubber bound to the filler, rubber bound to filler relative to the amount of rubber in the initial formulation The ratio was calculated.
2) Compound Mooney Viscosity: Using a Mooney viscometer, according to JIS K6300-1, after preheating at 130 ° C. for 1 minute, the rotor was rotated at 2 revolutions per minute, and the viscosity after 4 minutes was measured.
3) Tensile strength: measured by the tensile test method of JIS K6251.
4) Viscoelastic parameters: Viscoelastic parameters were measured in a torsion mode using a viscoelasticity test apparatus “ARES” manufactured by Rheometrics Scientific. Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. Larger values indicate better wet grip performance. Further, tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. A smaller value indicates better fuel economy performance. The difference between G ′ at strains of 0.1% and 10% was set as ΔG ′, which was used as an indicator of the pain effect. The smaller the value, the better the dispersibility of the filler such as silica.
5) Abrasion resistance: Using an Akron abrasion tester, the wear amount at a load of 6 pounds and 1000 revolutions was measured and indexed. A larger index indicates better wear resistance.

  As shown in Examples 3 and 4 of Table 2, the conjugated diene polymer produced according to the present invention has an increased amount of bound rubber in the silica blend composition, has a small Payne effect and excellent silica dispersibility, and high temperature. The tan δ of the tire is low and the hysteresis loss is small, and the tire has low rolling resistance, that is, excellent fuel economy. Moreover, it turns out that the balance of fuel-consumption property and wet skid resistance is excellent. Also, wear resistance and tensile strength are good.

[Examples 5 and 6 and Comparative Examples 5 and 6]
Using the samples shown in Table 1 (sample A to sample D) as raw rubber, a rubber composition was obtained with the following composition.
Modified conjugated diene polymer 100.0 parts by mass Silica (Ultrasil VN3 manufactured by Degussa) 25.0 parts by mass Carbon black (N339) 20.0 parts by mass Silane coupling agent (Si69 manufactured by Degussa) 2.5 parts by mass S -RAE oil (JOMO process NC140 manufactured by Japan Energy) 5.0 parts by weight zinc white 3.0 parts by weight stearic acid 2.0 parts by weight anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine) 1 1.0 part by weight sulfur 1.9 parts by weight vulcanization accelerator (N-cyclohexyl-2-benzothiazylsulfinamide) 1.0 part by weight vulcanization accelerator (diphenylguanidine) 1.5 parts by weight total 162.9 parts by weight Part Kneading, molding and vulcanization were carried out in exactly the same manner as in Examples 3 and 4. The physical property measurement results are shown in Table 3.

  As shown in Examples 5 and 6 in Table 3, the conjugated diene polymer produced according to the present invention increases the amount of bound rubber even in a composition in which silica and carbon black are blended to the same extent, and the pain effect is small. The dispersibility of silica is excellent, the high temperature tan δ is low, the hysteresis loss is small, and the tire has low rolling resistance, that is, low fuel consumption. Moreover, it turns out that the balance of fuel-consumption property and wet skid resistance is excellent. Also, wear resistance and tensile strength are good.

  The modified conjugated diene polymer of the present invention is excellent in affinity with an inorganic filler, and a rubber composition having excellent performance can be obtained. When used as a material for tire treads, tire treads with excellent physical properties such as wet skid characteristics, low hysteresis loss, wear resistance, and fracture strength, and workability, regardless of the type and combination of fillers to be blended. can get.

Claims (4)

After (co) polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as an initiator, the active terminal is represented by the general formula (1) compounds having two or more epoxy groups (a) are reacted, to all or a portion of the epoxy groups are further remaining 3 having a primary or secondary amino groups and one or more alkoxysilyl group -Aminopropyltriethoxysilane, N- (2-
Aminoethyl) -3-aminopropyltriethoxysilane, (3-trimethoxysilylpropyl)
(Lopyl) A process for producing a modified conjugated diene polymer characterized by reacting a compound (B) selected from diethylenetriamine .
(Where R1 and R2 are hydrocarbon groups having 1 to 10 carbon atoms or ether and / or hydrocarbon groups having a tertiary amine, and R3 and R4 are hydrogen, carbon atoms having 1 to 20 carbon atoms. A hydrogen group, or a hydrocarbon group having 1 to 20 carbon atoms having an ether and / or a tertiary amine, R5 is a hydrocarbon group having 1 to 20 carbon atoms, or at least one of ether, tertiary amine, epoxy, carbonyl, and halogen. (It is a C1-C20 hydrocarbon group which has 1 type of group, and n is an integer of 1-6.) (Co) polymerization of conjugated diene compounds or conjugated diene compounds and aromatic vinyl compounds
The compound (A) having two or more epoxy groups represented by the general formula (1) is bonded to the end of the body by ring opening of at least one epoxy group, and another epoxy of the compound (A) 3-aminopropyltriethoxysilane having a primary or secondary amino group and one or more alkoxysilyl groups for all or part of the group, N- (2-aminoethyl) -3-aminopropyltriethoxy A modified conjugated diene-based heavy compound having a Mooney viscosity (100 ° C., 1 + 4 minutes) of 20 to 100, in which a compound (B) selected from silane and (3-trimethoxysilylpropyl) diethylenetriamine is bonded by ring opening of an epoxy group Coalescence.
(Where R1 and R2 are hydrocarbon groups having 1 to 10 carbon atoms or ether and / or hydrocarbon groups having a tertiary amine, and R3 and R4 are hydrogen, carbon atoms having 1 to 20 carbon atoms. A hydrogen group, or a hydrocarbon group having 1 to 20 carbon atoms having an ether and / or a tertiary amine, R5 is a hydrocarbon group having 1 to 20 carbon atoms, or at least one of ether, tertiary amine, epoxy, carbonyl, and halogen. (It is a C1-C20 hydrocarbon group which has 1 type of group, and n is an integer of 1-6.) A modified conjugated diene polymer composition comprising 100 parts by mass of the polymer containing the modified conjugated diene polymer according to claim 2 and 1 to 200 parts by mass of a filler. The modified conjugated diene polymer composition according to claim 3, wherein the filler contains carbon black and / or silica.