JP5959172B2 - Modified conjugated diene polymer and production method thereof, modified conjugated diene polymer composition and production method thereof, and tire and production method thereof - Google Patents

Description

  The present invention relates to a method for producing a modified conjugated diene polymer and a modified conjugated diene polymer composition.

  In recent years, in connection with social demands for energy saving, demands for reducing fuel consumption of automobiles are becoming more severe. In order to meet such demands, further reduction in rolling resistance is also demanded for tire performance. As a technique for reducing the rolling resistance of the tire, there is a technique of optimizing the tire structure, and the technique using a material having less heat generation as the rubber composition is the most common.

  In order to obtain such a rubber composition having a low exothermic property, a silica filler is generally blended with a rubber-like polymer. However, since the interaction between the rubber-like polymer and the silica is usually very weak, there is a problem that the silica is difficult to disperse and a large torque is required during the kneading process, which makes it difficult to process.

  A modified conjugated diene obtained by modifying an active terminal of a conjugated diene polymer obtained by anionic polymerization of a conjugated diene monomer using an organolithium compound as a polymerization initiator as a rubbery polymer for solving such problems. Based polymers have been proposed.

  Moreover, cis 1,4-polybutadiene is generally used as a raw material rubber for rubber compositions. For example, tire treads are used to improve wear resistance, mechanical properties, and flexibility at low temperatures, and because they have excellent performance in bending crack resistance, they are also widely used as raw material rubber on sidewalls. Yes.

  However, there are few examples of applying a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure, which is particularly important for rubber for tire sidewalls, rubber for treads, rubber for carcass and the like. Further, the modification effect in the rubber composition containing silica is not always sufficient. In particular, a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure has almost no modification effect due to the incorporation of silica.

  Therefore, in order to solve such drawbacks, the active terminus of the conjugated diene polymer having a high cis content obtained using the rare earth catalyst is reacted with an alkoxysilane derivative having a functional group that interacts with the filler. Thus, attempts have been made to obtain terminal-modified modified conjugated diene-based polymers and modification with alkoxysilane derivatives, and attempts have been made to add condensation accelerators to the reaction system (see, for example, Patent Documents 1, 2, and 3). ).

International Publication No. 03/046020 Pamphlet JP-A-2005-008870 JP 2010-121086 A

  However, in the conventional techniques including Patent Documents 1 to 3, the modification rate of the modified conjugated diene polymer cannot be sufficiently increased, and there is room for improvement. In particular, when a lanthanum series metal compound is used as an initiator in the polymerization reaction of a conjugated diene polymer, it tends to be particularly difficult to obtain a high modification rate.

  This invention is made | formed in view of said situation, and it aims at providing the manufacturing method which can obtain the modified conjugated diene type polymer of a high modification | denaturation rate.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used functionalized conjugated diene polymers having a high 1,4-structure ratio by using an amino group-containing compound having a specific structure as a modifier. It has been found that a group can be efficiently introduced and a modified conjugated diene polymer having a high modification rate can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
[1]
Using a lanthanum series metal compound as an initiator, polymerizing a conjugated diene monomer to obtain a conjugated diene polymer;
Reacting the conjugated diene polymer, an alkoxy group bonded to a silyl group, and an amino group-containing compound each having at least one ester group;
A process for producing a modified conjugated diene-based polymer.
[2]
The method for producing a modified conjugated diene polymer according to [1], wherein the amino group-containing compound is a compound represented by the following formula (1).
(In Formula (1), R < ¹ > -R < ⁴ > represents a C1-C20 alkyl group or an aryl group each independently, R < ⁵ > and R < ⁶ > represent a C1-C20 alkylene group, R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.)
[3]
A modified conjugated diene polymer obtained by the production method according to [1] or [2].
[4]
100 parts by mass of a rubber component containing 10 parts by mass or more of the modified conjugated diene polymer according to [3],
0.5 to 300 parts by mass of a silica-based inorganic filler,
A modified conjugated diene polymer composition comprising:
[5]
A tire comprising the modified conjugated diene polymer composition according to [4].

  According to the present invention, it is possible to provide a production method capable of obtaining a modified conjugated diene polymer having a high modification rate.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

  The method for producing the modified conjugated diene polymer of the present embodiment includes a step of obtaining a conjugated diene polymer by polymerizing a conjugated diene monomer using a lanthanum series metal compound as an initiator, and a polymerization step. A step (modification step) of reacting the conjugated diene polymer, an alkoxy group bonded to a silyl group, and an amino group-containing compound each having at least one ester group. By using a lanthanum series metal compound as an initiator and a compound having at least one alkoxy group bonded to an ester group and a silyl group as a modifier, a conjugated diene polymer having a high 1,4-structure ratio can be obtained. It becomes possible to introduce a functional group at the terminal, and a modified conjugated diene polymer having a high modification rate can be easily produced.

(Initiator)
In this embodiment, a lanthanum series metal compound is used as an initiator for polymerizing a conjugated diene monomer. By using a lanthanum series metal compound as an initiator, a conjugated diene polymer having a high 1,4-structure ratio can be obtained. The lanthanum series metal compound to be used is not particularly limited as long as it can initiate the polymerization reaction of the conjugated diene monomer, and (a) an organic compound of a lanthanum series element, (b) an organoaluminum compound. And (c) a composite catalyst comprising a halogen-containing Lewis acid compound is preferred. A conjugated diene polymer can be obtained by bulk polymerization or solution polymerization in a hydrocarbon solvent in the presence of this composite catalyst (polymerization step).

Examples of the organic compound of the (a) lanthanum series element include compounds represented by the formula LnY ₃ (wherein Ln represents a lanthanum series element and Y represents an acid residue).
Here, Ln represents a lanthanum series element. Specifically, as a lanthanum series element in the periodic table having an atomic number of 57 to 71, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dys Prodium, holmium, erbium, thulium, ytterbium and lutetium. Among these, lanthanum, cerium, praseodymium, neodymium and gadolinium are preferable from the viewpoint of polymerization activity, and neodymium is more preferable from the viewpoint of the balance between polymerization activity and industrial availability.
Y represents an acid residue and is a salt of alcohol, phenol, thioalcohol, thiophenol, amine, carboxylic acid, organic phosphoric acid, or organic phosphorous acid. It is preferable from the viewpoint. These organic compounds of lanthanum series elements may be used alone or in a mixture of two or more.

Examples of (a) alcohol compounds (alkoxides) and phenolic compounds (phenoxides) of lanthanum series elements include compounds represented by the formula Ln- (OR ^a ) ₃ . Here, R ^a represents a hydrocarbon group, and from the viewpoint of easy handling, preferably an alkyl group, alkenyl group, alkyl-substituted or alkenyl-substituted phenyl group, or alkyl-substituted or alkenyl group having 1 to 40 carbon atoms. A substituted naphthyl group; The alkyl group and alkenyl group may be linear, branched, or cyclic. Specific examples of preferable alcohol and phenol used for alkoxide and phenoxide include 2-ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, nonylphenol, benzine alcohol and the like.

(A) Examples of the thioalcohol compound (thioalkoxide) and the thiophenol compound (thiophenoxide) of the lanthanum series element include compounds represented by the formula Ln (SR ^b ) ₃ . Here, R ^b represents a hydrocarbon group, and from the viewpoint of easy handling, preferably an alkyl group, alkenyl group, alkyl-substituted or alkenyl-substituted phenyl group, or alkyl-substituted or alkenyl group having 1 to 40 carbon atoms. A substituted naphthyl group; The alkyl group and alkenyl group may be linear, branched, or cyclic.

(A) Examples of amine compounds of lanthanum series elements include compounds represented by the formula Ln (NR ^c ₂ ) ₃ . Here, R ^c represents a hydrocarbon group, and from the viewpoint of easy handling, preferably an alkyl group, alkenyl group, alkyl-substituted or alkenyl-substituted phenyl group, or alkyl-substituted or alkenyl group having 1 to 40 carbon atoms. A substituted naphthyl group; The alkyl group and alkenyl group may be linear, branched, or cyclic.

Examples of (a) carboxylic acid compounds of lanthanum series elements include compounds represented by the formula Ln (OCOR ^d ) ₃ . Here, R ^d represents a hydrocarbon group, and from the viewpoint of ease of handling, preferably an alkyl group, alkenyl group, alkyl-substituted or alkenyl-substituted phenyl group, or alkyl-substituted or alkenyl-substituted naphthyl in the range of 1 to 40 It is a group. The alkyl group and alkenyl group may be linear, branched, or cyclic. The carboxyl group may be any of primary, secondary and tertiary bonds to the hydrocarbon. Specific examples of preferable carboxylic acids include octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, and isostearic acid (2- (1,3,3-trimethylbutyl) -5,7,7-trimethyloctanoic acid). , Benzoic acid, naphthenic acid, versatic acid mainly having 10 carbon atoms (commercially available product, for example, “Versatic acid 10” manufactured by Shell Chemical Co., Ltd.). A carboxylic acid having a branch at the α-position is preferable from the viewpoint of solubility, and specific examples include 2-ethyl-hexanoic acid, isostearic acid, 2-isopropyl-5-methylhexanoic acid, and versatic acid.

(A) As an organic phosphate compound of a lanthanum series element, for example, a compound represented by the formula Ln (OPOR ^e R ^f ) ³ may be mentioned. Here, R ^e and R ^f each independently represent a hydrocarbon group, and from the viewpoint of ease of handling, preferably an alkyl group, an alkenyl group, an alkyl-substituted or alkenyl-substituted phenyl group in the range of 1 to 40, Or an alkyl-substituted or alkenyl-substituted naphthyl group. The alkyl group or alkenyl group may be linear, branched or cyclic. From the viewpoint of polymerization activity, specific examples of preferable organic phosphate compounds include tris (di-2-ethylhexyl phosphate) and tris (dinonylphenyl phosphate).

Examples of the organic phosphorous acid compound (a) lanthanides, for example, a compound represented by the formula Ln (OPR ^g R ^h) ₃ and the like. Here, R ^g and R ^h each independently represent a hydrocarbon group, and from the viewpoint of easy handling, preferably an alkyl group having 1 to 40 carbon atoms, an alkenyl group, an alkyl-substituted or alkenyl-substituted phenyl group, Or an alkyl or alkenyl-substituted naphthyl group. The alkyl group or alkenyl group may be linear, branched, or cyclic. From the viewpoint of polymerization activity, specific examples of preferred organic phosphite compounds include tris (di-2-ethylhexyl phosphite) and tris (dinonylphenyl phosphite).

  Among the organic compounds of the above (a) lanthanum series elements, from the viewpoint of solubility in an organic solvent, a carboxylic acid compound and an organic phosphoric acid compound are preferable, and a carboxylic acid compound is more preferable. In addition, the organic compound of the lanthanum series element may be a composite salt of two or more kinds of the above-described compounds, for example, a composite salt of the above-described carboxylic acid compound and an organic phosphoric acid compound.

(B) The organoaluminum compound is not particularly limited, but is preferably a compound represented by the formula AlR ⁱ _(3-m) H _m from the viewpoint of polymerization activity. Here, R ⁱ is an aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms; or 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Represents an alkyl-substituted or alkenyl-substituted aromatic hydrocarbon group. m is 0, 1 or 2, preferably 0 or 1, and H represents a hydrogen atom. The organoaluminum compound may be an alumoxane compound (a compound having a direct bond between carbon and aluminum and also having a direct bond between oxygen and aluminum).

  Specific examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diethylaluminum dihydride, diisobutylaluminum hydride, ethylaluminum dihydride, isobutylaluminum dihydride. , Methylalumoxane, ethylalumoxane, isobutylalumoxane, butylalumoxane, hexylalumoxane, octylalumoxane, and the like. More preferred specific examples include triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride. , Methylalumoxa , Ethyl alumoxane, butyl alumoxane, isobutyl alumoxane, t- butyl alumoxane, hexyl alumoxane, octyl alumoxane. These may be used alone or as a mixture of two or more.

  (C) Examples of the halogen element-containing Lewis acid compound include halogen compounds of elements belonging to Group IIIb, IVb or Vb of the periodic table. From the viewpoint of polymerization activity, aluminum halides and organometallic halogens are preferred. A compound.

  The halogen element of the aluminum halide is preferably chlorine or bromine from the viewpoint of polymerization activity. Specific examples of the aluminum halide include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Examples include aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, and aluminum tribromide.

  Specific examples of the organometallic halide include dibutyltin dichloride, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride and tin tetrachloride.

  Among these, aluminum halides are preferable from the viewpoint of availability, and among them, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are more preferable. preferable.

  The amount and composition ratio of each component of the composite catalyst used in the production method of the present embodiment are not particularly limited and can be appropriately selected depending on the purpose. The amount of component (a) to be used is usually 0.005 to 2.5 mmol, preferably 0.025 to 0.5 mmol, relative to 1 mol of the conjugated diene monomer. The usage-amount of the component (b) with respect to 1 mol of conjugated diene type monomers is 0.05-25 mmol normally, Preferably it is the range of 0.25-5 mmol. The amount of component (c) used per mole of conjugated diene monomer varies depending on the number of halogen atoms contained in the molecule, and is expressed as the number of halogen atoms relative to 1 mole of lanthanum series element (Ln). Atom / Ln = 1 to 6, preferably 2 to 4.

(Monomer)
The conjugated diene monomer that can be used by the production method of the present embodiment is not particularly limited. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3- Examples thereof include conjugated diene compounds having 4 to 8 carbon atoms such as pentadiene (piperylene) and 2,3-dimethyl-1,3-butadiene, or mixtures thereof. Among these, butadiene is preferable from the viewpoint of polymerization activity and usefulness of the resulting polymer.

  In the present embodiment, a conjugated diene copolymer obtained by copolymerizing the above-described conjugated diene monomer and other monomers can also be used. Other monomers copolymerizable with the conjugated diene monomer include, for example, vinyl aromatic monomers such as styrene, α-methylstyrene, p-methylstyrene, vinylethylbenzene; methyl (meth) acrylate (Meth) acrylic acid monomers such as butyl (meth) acrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. The blending ratio of the conjugated diene monomer and the other monomer is not particularly limited, but from the viewpoint of the usefulness of the polymer obtained, the conjugated diene monomer may be 50 to 100% by mass. More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%.

(Impurities in the monomer)
In general, the conjugated diene monomer may contain impurities such as acetylenes, allenes, and aldehydes. Examples of the acetylenes include 1-butyne and vinylacetylene, and examples of the allenes include propadiene and 1,2-butadiene. Therefore, it is preferable to perform a step (purification step) of purifying the conjugated diene monomer before the polymerization reaction of the conjugated diene compound. In the purification step, the total amount of acetylenes and allenes contained as impurities in the monomer is preferably 50 ppm or less, and more preferably 20 ppm or less. The purification method is not particularly limited, and for example, methods such as hydrogenation and distillation can be employed. Such a purification step further increases the activity of the polymer terminal and further increases the yield of the modification reaction.

(solvent)
The production method of this embodiment is usually carried out by bulk polymerization or solution polymerization. As a polymerization solvent that can be used when the solution polymerization method is used, generally, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane (isohexane), n-heptane, cyclohexane, methylcyclopentane, benzene An aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon having a boiling point of 200 ° C. or lower, such as toluene, is preferable. The polymerization solvent may be a single type or a mixture of two or more types. Furthermore, it is also possible to use mixed solvents including halogenated hydrocarbons such as methylene chloride and chlorobenzene, aprotic polar organic solvents such as ketone compounds, ether compounds, and trialkylamine compounds. The solubility of the composite catalyst in the polymerization solvent and the polymerization activity can be further improved by appropriately selecting the solvent according to the catalyst to be used.

(Polymerization conditions, temperature)
The polymerization temperature in the manufacturing method of this embodiment is not specifically limited, Usually, it is -30-150 degreeC, Preferably it is 10-120 degreeC, More preferably, it is 30-100 degreeC. As the polymerization temperature increases, the polymerization rate and the polymerization rate increase, and the microstructure of the resulting polymer tends to increase the amount of vinyl bonds. On the other hand, when the polymerization temperature is lowered, the activity rate of the polymer terminal is increased, and the modification rate in the modification reaction described later tends to be increased.

  The polymerization reaction type is not particularly limited, and can be used in either a batch method or a continuous method. In addition, in the production method of this embodiment, it is possible to carry out a preliminary reaction or aging reaction of some or all of the catalyst components in the presence or absence of a conjugated diene monomer prior to polymerization. It is. As aging conditions, (a) an organic compound of a lanthanum series element, (b) an organoaluminum compound, and (c) a halogen-containing compound in an inert solvent in the presence or absence of a conjugated diene monomer to be polymerized The components of the Lewis acid compound are mixed. The aging temperature is -50 to 80 ° C, preferably -10 to 50 ° C, and the aging time is 0.01 to 24 hours, preferably 0.05 to 5 hours, particularly preferably 0.1 to 1 hour.

(Micro structure)
The conjugated diene polymer obtained by the polymerization process of the present embodiment is mainly composed of 1,4-bonds, and conjugated diene polymers having few vinyl bonds (that is, 1,2-bonds and 3,4-bonds). can do. For example, the term “1,4-bond mainly” as used herein means that the amount of 1,4-bond in the polymer is 80% or more, preferably 90% or more, more preferably 95% or more. is there. That is, the microstructure of the obtained conjugated diene polymer preferably has a 1,4-bond amount of 90% or more and a vinyl bond amount of 10% or less. The microstructure changes depending on conditions such as the composition of the initiator and the polymerization temperature. In particular, when an initiator containing neodymium is used, the ratio of cis bonds among 1,4-bonds tends to increase. Therefore, when an initiator containing neodymium is used, 1, 1 of the resulting conjugated diene polymer is obtained. 4- The amount of bonds is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In this embodiment, the microstructure here is measured using an infrared spectrophotometer.

(Modifier)
In the production method of this embodiment, after the polymerization reaction described above achieves a predetermined polymerization rate, the obtained conjugated diene polymer, an alkoxy group bonded to a silyl group, and an ester group each have at least one. Reaction with an amino group-containing compound (modification step). By this step, a modified conjugated diene polymer can be obtained efficiently. Specifically, 1- [2- (methoxycarbonyl) ethyl] -4- [3- (trimethoxysilyl) propyl] piperazine, 1- [2- (ethoxycarbonyl) ethyl] -4- [3- (tri Ethoxysilyl) propyl] piperazine, 1- [2- (methoxycarbonyl) ethyl] -3- [3- (trimethoxysilyl) propyl] imidazolidine, 1- [2- (ethoxycarbonyl) ethyl] -3- [3 -(Triethoxysilyl) propyl] imidazolidine and the like.

  In the reaction between the conjugated diene polymer and the amino group-containing compound, after the predetermined polymerization rate is achieved, the conjugated diene polymer and the amino group-containing compound are mixed and reacted. The predetermined polymerization rate can be appropriately set according to the physical properties of the desired modified conjugated diene polymer, but preferably after reaching a polymerization rate of 90% or more, more preferably 95% or more. It is preferable to react with an amino group-containing compound. By reacting under such conditions, a uniform polymer having a narrow molecular weight distribution tends to be obtained. Further, if necessary, the amino group-containing compound can be divided or continuously added at a polymerization rate of 30 to 90% for reaction. In that case, a polymer having a wide molecular weight distribution and a high modification rate tends to be obtained.

A preferable modifier is a compound represented by the formula (1). By using the compound represented by Formula (1) as a modifier, it can efficiently react with the active terminal of the conjugated diene polymer. As a result, the functional group can be efficiently introduced into the terminal of the conjugated diene polymer, and the modification rate can be increased.
(In the formula ^(1), R 1 ~R ⁴ represents an alkyl group or an aryl group having 1 to 20 carbon atoms each independently, R ⁵ and R ⁶ represents an alkylene group having 1 to 20 carbon atoms. R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.)

  Conventionally, a conjugated diene polymer obtained by using a lanthanum series metal compound as an initiator is a living polymer (living polymer). Due to the influence of the coordination compound around the terminal, the reactivity to the functional group to be introduced in the modification step is not sufficient. For this reason, there is a problem that the type of functional group of the modifier affects the modification rate of the modification reaction. However, the present inventors have surprisingly found that a modified conjugated diene polymer having a high modification rate can be easily obtained by using an amino group-containing compound having a specific structure as a modifier in the modification step.

  The amino group-containing compound used as a modifier in this embodiment has a structure having at least one alkoxy group bonded to a silyl group and an ester group, and is very reactive with the polymerization active terminal of the conjugated diene polymer. Have high ester groups. For this reason, compared with the conventionally used modifier, the amino group-containing compound of the present embodiment and the active end of the conjugated diene polymer are more easily bonded, and thus has a higher affinity with the silica-based inorganic filler. A modified conjugated diene polymer in which an alkoxy group bonded to a silyl group is introduced at a high modification rate can be obtained. Therefore, when the composition of the modified conjugated diene polymer and silica inorganic filler of this embodiment is used as a raw material rubber for tires, the filler has excellent dispersibility, fuel saving, and wear resistance. become. Among these, the modifier represented by the formula (1) is particularly preferable.

  Examples of the compound represented by the formula (1) include N- (2-methoxycarbonyl) methyl-N-methyl-3-aminomethyltrimethoxysilane, N- (2-methoxycarbonyl) methyl-N-methyl- 3-aminoethyltrimethoxysilane, N- (2-methoxycarbonyl) methyl-N-methyl-3-aminopropyltrimethoxysilane, N- (2-ethoxycarbonyl) methyl-N-methyl-3-aminomethyltriethoxy Silane, N- (2-ethoxycarbonyl) methyl-N-methyl-3-aminoethyltrioxysilane, N- (2-ethoxycarbonyl) methyl-N-methyl-3-aminopropyltriethoxysilane, N- (2 -Ethoxycarbonyl) ethyl-N-trimethylsilyl-3-aminopropyltriethoxysilane and the like That. Among these, a modified conjugated diene polymer modified with N- (2-ethoxycarbonyl) ethyl-N-trimethylsilyl-3-aminopropyltriethoxysilane recovers the polymer by solvent removal by steam stripping or the like. Thus, the N-trimethylsilyl group is hydrolyzed to produce a secondary amino group, which is preferable because the interaction with the silica-based inorganic filler and carbon is further strengthened.

  The amount of the amino group-containing compound used is not particularly limited, but the molecular weight of the resulting modified conjugated diene polymer is 0.5 to 1 mol with respect to 1 mol of the active terminal of the conjugated diene polymer. Therefore, it is preferable. Of course, the addition amount of the modifier can be appropriately adjusted according to the desired modification ratio.

  The amino group-containing compound may be added alone or as a solution dissolved in an inert hydrocarbon or the like. The amino group-containing compound may be added all at once, or may be added separately or continuously. The modification reaction is usually performed at a temperature close to the polymerization temperature for several minutes to several hours. The reaction time is preferably 5 minutes to 2 hours.

  The modified conjugated diene polymer obtained by the production method of the present embodiment has a high modification rate. The modification rate mentioned here is a comparison with GPC using polystyrene gel as a filler by utilizing the property that the modified polymer adsorbs on a gel permeation chromatography (GPC) column using silica gel as a filler. Measured. The modification rate of the modified conjugated diene polymer obtained by the production method of the present embodiment is not particularly limited and can be appropriately adjusted according to the desired physical properties, but is preferably 20% or more, more preferably 30%. As mentioned above, More preferably, it can be 50% or more.

(Oil exhibition)
The modified conjugated diene polymer of the present embodiment may be made into an oil-extended polymer by adding process oil as needed before the solvent removal step. The process oil is not particularly limited, but from the viewpoint of compatibility, aroma oil, naphthene oil, paraffin oil, aroma substitute oil having a polycyclic aromatic component of 3% by mass or less by IP346 method, and the like are preferable. Among these, it is preferable to use an aroma substitute oil having a polycyclic aromatic component of 3% by mass or less from the viewpoint of environmental safety, prevention of oil bleed, and wet grip characteristics. Aroma substitute oils include, for example, Treated Distilled Aromatic Extract (TDAE), Mildly Medium Extracted, etc., as described in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999). or Special Residual Aromatic Extract (SRAE). The amount of the extender oil used is not particularly limited, and is usually 10 to 60 parts by mass with respect to 100 parts by mass of the modified conjugated diene polymer. From the viewpoint of preventing oil bleed and workability of the product, 20 It is preferably ˜37.5 parts by mass.

(Finishing)
The modified conjugated diene polymer of this embodiment is added by a polymerization terminator and a stabilizer, if necessary, to the reaction system, and known desolvation and drying operations used in the production of the conjugated diene polymer, for example, by steam stripping. Desolvation, compressed water squeezing machine such as screw extruder squeezing dehydrator, expander dehydrator, hot air dryer, etc., concentrating in flashing tank, and devolatilizing with vent extruder etc., directly with drum dryer etc. The polymer can be recovered by a method such as devolatilization. The polymerization terminator can be selected from water or a protic polar organic compound. Examples of the latter include various alcohols, phenols, and carboxylic acid compounds. The stabilizer can be selected from known conjugated diene polymer stabilizers and antioxidants. Particularly preferred examples of these include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2 , 4-bis (n-octylthiomethyl) -6-methylphenol, N, N′-dialkyldiphenylamine, N-alkyldiphenylamine and the like. The resulting polymer is usually formed into a veil.

(Combination)
The modified conjugated diene polymer of this embodiment is generally processed by a method usually used in the rubber industry and used as a rubber product. In this case, a modified conjugated diene polymer composition containing a rubber component containing the modified conjugated diene polymer obtained in this embodiment and a filler is preferable. The content of the modified conjugated diene polymer in 100 parts by mass of the rubber component is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. In addition to the filler, if necessary, it can be blended with other rubber materials and processed by adding a silane coupling agent, a rubber softener, a vulcanizing agent, a vulcanizing aid, and other additives. In blending, various mechanical mixers such as a Banbury mixer and a roll mill are used, and the modified conjugated diene polymer of this embodiment has a small torque during blending, and the dispersion of the filler even when the kneading time is short. Has the advantage of being good. Further, the tack of the blended fabric is excellent and suitable for processing rubber products.

(Other rubber materials)
Other rubber materials that can be blended are not particularly limited, and examples thereof include natural rubber and synthetic rubber. Examples of the synthetic rubber include low-cis polybutadiene, vinyl-cis-butadiene rubber (VCR), styrene-butadiene rubber (SBR), isoprene rubber, butyl rubber, and ethylene-propylene-diene rubber (EPDM).

  The amount of other rubber materials that can be blended is not particularly limited, but is preferably 0 to 900 parts by weight with respect to 100 parts by weight of the modified conjugated diene polymer, depending on the required performance of the elastomer obtained. The amount is more preferably 10 to 400 parts by mass, and still more preferably 50 to 300 parts by mass.

(Silica-based inorganic filler)
As the silica-based inorganic filler used in the modified conjugated diene-based polymer composition of the present embodiment, solid particles having SiO ₂ or Si ₃ Al as a main component of a structural unit can be used. Examples thereof include inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, and the like. Further, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable, and silica is more preferable.

  As silica, dry silica, wet silica, synthetic silicate silica, and the like can be used. Among them, wet silica is most preferable because it has the most remarkable effect of improving fracture characteristics and wet skid resistance.

In the modified conjugated diene polymer composition of the present embodiment, from the viewpoint of obtaining practically good abrasion resistance and fracture characteristics, the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 170 to 300 m. ² / g is preferable, and 200 to 300 m ² / g is more preferable.

  Moreover, 0.5-300 mass parts is preferable with respect to 100 mass parts of said rubber components, and, as for the compounding quantity of a silica type inorganic filler, 5-200 mass parts is more preferable, and 20-100 mass parts is still more preferable. By adding the silica-based inorganic filler in an amount of 0.5 parts by mass or more, the effect of addition can be exhibited. Mechanical strength is obtained.

(Other ingredients)
<Carbon black>
Carbon black may be added to the modified conjugated diene polymer composition of this embodiment as a reinforcing filler other than the silica-based inorganic filler described above. Carbon black of SRF, FEF, HAF, ISAF, SAF, etc. can be used as the carbon black. Carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a DBP (dibutyl phthalate) oil absorption of 80 mL / 100 g. preferable.

  The blending amount of carbon black is preferably 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rubber component containing 10 parts by weight or more of the modified conjugated diene polymer. Part by mass is more preferable. In order to express the performance required for uses such as tires such as dry grip performance and conductivity, 0.5 parts by mass or more is preferably added, and from the viewpoint of dispersibility, it is preferably 100 parts by mass or less.

<Metal oxide, metal hydroxide>
In addition to the silica-based inorganic filler and carbon black described above, a metal oxide or metal hydroxide may be further added to the modified conjugated diene polymer composition of the present embodiment.

Metal oxide refers to solid particles having the chemical formula M _x O _y (M is a metal atom, x and y are each an integer of 1 to 6) as a main component, such as alumina, titanium oxide, and oxidation. Magnesium, zinc oxide, or the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide and the like.

  These reinforcing agents can be arbitrarily selected according to the required performance. Moreover, 2 or more types can be mixed and used as needed.

  The compounding amount of the metal oxide and / or metal hydroxide is 0 with respect to 100 parts by mass of the rubber component containing 10 parts by mass or more of the modified conjugated diene polymer from the viewpoint of processability and performance of the resulting composition. 5-100 mass parts is preferable, 3-100 mass parts is more preferable, and 5-50 mass parts is still more preferable.

(Silane coupling agent)
The silane coupling agent has a function of tightly interacting the above-described rubber component and silica-based inorganic filler, and has an affinity or binding property to each of the rubber component and the silica-based inorganic filler. It is. As the silane coupling agent, a compound having a sulfur bond part and an alkoxysilyl group part in one molecule is generally used.

  The silane coupling agent that can be used is not particularly limited. For example, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (Triethoxysilyl) -ethyl] -tetrasulfide and the like.

  The addition amount of the silane coupling agent is not particularly limited, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the silica-based inorganic filler from the viewpoints of effects and economy. More preferably, it is -5 mass parts.

(Rubber softener)
As the rubber softener, mineral oil or liquid or low molecular weight synthetic or vegetable softener is preferably used. The type of rubber softener is not particularly limited, but from the viewpoint of compatibility and environmental safety, aroma oil, naphthenic oil, paraffin oil, aroma substitute oil containing 3% by mass or less of polycyclic aromatic component by IP346 method Etc.

  Although the addition amount of the rubber softener is not particularly limited, it is preferably 5 to 150 parts by mass, and 5 to 100 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoints of effects and economy. Is more preferable.

(Vulcanizing agent, etc.)
As the vulcanizing agent, radical initiators, sulfur, sulfur compounds and the like are used. Examples of the radical initiator include peroxides such as peroxyketals and dialkyl peroxides. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Examples of the sulfur compound include sulfur monochloride, sulfur dichloride, and organic polysulfide.

  Furthermore, a vulcanization auxiliary and a vulcanization accelerator can be used together as necessary. As the vulcanization aid, zinc white, stearic acid or the like is used. As the vulcanization accelerator, various known vulcanization accelerators are used. Guanidine vulcanization accelerators, thiourea vulcanization accelerators, thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamides A system vulcanization accelerator or the like is used.

  As other additives, anti-aging agents, waxes, conductive agents, colorants and the like are used. Examples of the anti-aging agent include p-phenylenediamine, naphthylamine, diphenylamine, quinoline, and phenol. Examples of the wax include paraffinic petroleum wax. Examples of the conductive agent include metal powder, graphite, carbon fiber, and the like. Examples of the colorant include pigments and dyes.

(Manufacture of vulcanized rubber products)
The modified conjugated diene-based polymer of the present embodiment is blended with the above-described components and the like as necessary to form a composition and vulcanized for use in the production of various rubber products. In particular, it is optimally used as a raw material rubber for tires, and preferably a tire containing the modified conjugated diene polymer of this embodiment. For example, when used for sidewalls, it has excellent resistance to bending cracks and low heat generation.When used for treads, it has excellent fuel economy and wear resistance, flexibility at low temperatures, and when used for carcass. Since it is excellent in low exothermic property and bending crack resistance, both are preferably used. As other uses, it is also suitably used as a material for various industrial articles and shoe soles.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The analysis method was performed by the following method.
(1) 1,4-cis content Measured using an infrared spectrophotometer and obtained by data processing by the Morero method.
(2) Mooney Viscosity According to JIS K6300-1, using an L-shaped rotor, preheating was performed for 1 minute, and the viscosity after 4 minutes was measured. The measurement temperature was 100 ° C.

(3) Number average molecular weight, weight average molecular weight, molecular weight distribution Chromatogram was measured using gel permeation chromatography (GPC) used by connecting three columns with polystyrene gel as a filler, and standard polystyrene was measured. From the relationship between the retention capacity and molecular weight obtained from the calibration curve used, the frequency for all peak areas in each molecular weight range is calculated according to the conventional method, and the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution are calculated. did.
Tetrahydrofuran (THF) was used as the eluent.
The column is a guard column; manufactured by Tosoh Corporation, “TSK guard column HHR-H”, the column: manufactured by Tosoh Corporation “TSK-Super H 7000”, “TSK-Super H 6000”, “TSK-Super H 5000”, oven temperature : 40 ° C., THF flow rate 0.6 mL / min, manufactured by Tosoh Corporation: HLC-8020, detector; RI was used.
A sample for measurement was measured by injecting 20 μL using 10 mg dissolved in 20 mL of THF.

(4) Modification rate Applying the property that the modified component is adsorbed on a GPC column using silica gel as a filler, using a sample solution containing a sample and a low molecular weight internal standard polystyrene molecular weight of 5000 (polystyrene does not adsorb), GPC (manufactured by Tosoh Corporation: HLC-8020) and a silica-based column (guard column; “DIOL” 4.6 × 12.5 mm 5 micron, column) used in (3) above. GPC (Tosoh Corporation: “CCP8020” series build-up type GPC system) of “Zorbax PSM-1000S”, “PSM-300S”, “PSM-60S”, oven temperature: 40 ° C., THF flow rate 0.5 mL / min) "AS-8020", "SD-8022", "CCPS", "CO-8020", "RI-" Both chromatograms of 8021 ") were measured, the amount of adsorption to the silica column was measured from the difference between them based on the internal standard polystyrene peak, and the coupling reaction rate was determined.
As a sample for measurement, in common, 10 mg of a measurement object was dissolved in 20 mL of THF together with 5 mg of standard polystyrene, and 200 μL was injected for measurement.
Specifically, the total peak area of the chromatogram using the polystyrene column is 100, the peak area of the sample polystyrene is P1, the peak area of the standard polystyrene is P2, and the peak area of the chromatogram using the silica column is The total was 100, the sample peak area was P3, the peak area of standard polystyrene was P4, and the modification rate was calculated by the following formula.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100

[Example 1]
The inside of the fully dried 300 mL pressure-resistant mini cylinder was sufficiently replaced with dry nitrogen. There, 130 mL of a 20% by mass cyclohexane solution containing 20 g of 1,3-butadiene, and isostearic acid (manufactured by Wako Pure Chemical Industries, Ltd., 2- (1,3,3-trimethylbutyl) -5,7,7 -Trimethyloctanoic acid) sodium salt and neodymium chloride were reacted with 11.7 mL of a 30% by mass cyclohexane solution containing 2.7 mmol of neodymium isostearate, and shaken at room temperature for 5 minutes. Subsequently, 22.5 mL of a 1 molar hexane solution containing 22.5 mmol of diisobutylaluminum hydride was further added and shaken, and then allowed to stand for 5 minutes. An initiator solution was prepared by adding 8.1 mL of a 1 molar hexane solution of ethylaluminum sesquichloride so that Cl / Nd (molar ratio) = 3 was shaken, and then allowed to stand for 20 minutes.
Next, the inside of the pressure-resistant autoclave with a stirrer having an inner volume of 11 L that was sufficiently dried was sufficiently replaced with dry nitrogen. Thereto, 6 kg of a cyclohexane mixed solution containing 900 g of 1,3-butadiene was charged into an autoclave, 170 mL of an initiator solution prepared in advance was added, and polymerization was carried out at 50 ° C. for 2 hours. After the polymerization reaction, 3.8 mmol of N- (2-ethoxycarbonyl) ethyl-N-trimethylsilyl-3-aminopropyltriethoxysilane as a modifier was added and reacted at 50 ° C. for 1 hour. Thereafter, 100 mL of a methanol / siloxane solution (30/70) containing 5 g of 2,6-bis (tert-butyl) -4-methylphenol was added to stop the reaction. The solvent was removed using a drum dryer to obtain a polymer A. Table 1 shows the analysis results of the obtained polymer A.

[Example 2]
The polymer B was prepared in the same manner as in Example 1 except that the addition amount of N- (2-ethoxycarbonyl) ethyl-N-trimethylsilyl-3-aminopropyltriethoxysilane as a modifier was changed to 2.8 mmol. Got. Table 1 shows the analysis results of the obtained polymer B.

[Comparative Example 1]
Except for using 2.2 mmol of neodymium isostearate and 18 mmol of diisobutylaluminum hydride and using 11 mmol of 3-glycidoxypropyltrimethoxysilane (trade name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) as a modifier. 1 to obtain a polymer C. The measurement results of the obtained polymer C are shown in Table 1. In the case of the modifier having no ester group, the terminal of the polymer was not modified at all, and the modification rate was zero.

[Comparative Example 2]
The inside of the fully dried 300 mL pressure-resistant mini cylinder was sufficiently replaced with dry nitrogen. There, 130 mL of a 20% by mass cyclohexane solution containing 20 g of 1,3-butadiene, and isostearic acid (manufactured by Wako Pure Chemical Industries, Ltd., 2- (1,3,3-trimethylbutyl) -5,7,7 -Trimethyloctanoic acid) sodium salt and neodymium chloride were reacted with 1.9 mL of a 30% by mass cyclohexane solution containing 2.1 mmol of neodymium isostearate and shaken at room temperature for 5 minutes. Subsequently, 22.5 mL of a 1 molar hexane solution containing 22.5 mmol of diisobutylaluminum hydride was further added and shaken, and then allowed to stand for 5 minutes. After adding 6.3 mL of 1 molar hexane solution of ethylaluminum sesquichloride to Cl / Nd (molar ratio) = 3 and shaking, an initiator solution was prepared by allowing to stand for 20 minutes.
Next, the inside of the pressure-resistant autoclave with a stirrer having an inner volume of 11 L that was sufficiently dried was sufficiently replaced with dry nitrogen. Thereto, 6 kg of a cyclohexane mixed solution containing 900 g of 1,3-butadiene was charged into an autoclave, 167 mL of an initiator solution prepared in advance was added, and polymerization was carried out at 50 ° C. for 2 hours. After the polymerization reaction, 100 mL of a methanol / siloxane solution (30/70) containing 5 g of 2,6-bis (tert-butyl) -4-methylphenol was added to stop the reaction. The solvent was removed using a drum dryer to obtain a polymer D. Table 1 shows the analysis results of the obtained polymer D.

[Compound evaluation]
The raw materials are blended in the proportions shown in Table 2 below, set to a bath temperature of 130 ° C., and a raw rubber as a first-stage kneading using a pressure type kneader “D0.3-3 type” manufactured by Moriyama. (Conjugated diene polymer, styrene-butadiene (SBR; manufactured by Asahi Kasei Chemicals Corporation, “Asaprene E15” natural rubber (adjusted to Mooney viscosity 60 by mastication)), SRAE oil, silica (manufactured by Evonik Degussa, “Ultra” Zil VN3 ") and a silane coupling agent (Evonik Degussa," Si75 ") were added in this order and kneaded for 4 minutes.Then, dumped out at about 160 ° C, passed through a roll and cooled.

  Subsequently, as the second stage kneading, the remaining raw materials excluding sulfur and the vulcanization accelerator were added and kneaded for 3 minutes. Dumped out at about 160 ° C., passed through a roll and cooled.

  After cooling, using a roll, sulfur (manufactured by Hosoi Chemical Co., Ltd.) and a vulcanization accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd., “Noxeller CZ-G” and “Noxeller DP”) are added at 170 ° C. Vulcanization was performed under conditions of 12 minutes to obtain a vulcanized rubber. The formulation examples (S-1 to S-5) in each Example and Comparative Example are shown in Table 2, and the evaluation results of the performance of the vulcanized rubber obtained in each Example and each Comparative Example are shown in Table 3 and Table 4. Show.

The evaluation method was performed by the following method.
(1) Compound Mooney Viscosity The Mooney viscosity of the rubber compound before vulcanization described above was preheated for 1 minute at 100 ° C. using an L-shaped rotor according to JIS K6300-1 using a Mooney viscometer. Later, it was rotated at 2 revolutions per minute and the viscosity after 4 minutes was measured. When the Mooney viscosity was a small value, it was judged that the energy consumed during kneading was small and the processability was good.

(2) Bound rubber amount Formulation after completion of second stage kneading step: About 0.2 gram was cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight was measured. Then, after being immersed in toluene for 24 hours, a drying treatment was performed and the weight was measured. Calculate the amount of rubber bound to the filler (modified conjugated diene polymer, SBR, natural rubber) from the amount of undissolved components, and determine the ratio of the rubber bound to the filler to the amount of rubber in the first blend. It was. The larger the value, the more bound rubber.

(3) Tensile strength Vulcanized specimens were measured by the tensile test method of JIS K6251. It shows that it is excellent in fracture resistance, so that a numerical value is large.

(4) Viscoelasticity By using “ARES viscoelasticity tester” manufactured by TA Instruments and changing the strain in the case of low temperature (0 ° C.) and high temperature (50 ° C.) by the torsion method. The tan δ at a measurement frequency of 10 Hz was measured. In the case of low temperature (0 ° C.), tan δ was measured at a strain of 1%, and in the case of high temperature (50 ° C.), tan δ was measured at a strain of 0.1%, 3%, and 10%.
A higher tan δ (loss tangent) measured at a low temperature (0 ° C.) and a strain of 1% was judged to be superior in wet skid resistance (ie, grip performance). And it was judged that the lower the tan δ (loss tangent) measured at a high temperature (50 ° C.) and a strain of 3%, the smaller the hysteresis loss and the better the tire's low rolling resistance (that is, fuel efficiency).
The dispersibility of the filler was evaluated based on the difference ΔG ′ between G ′ when the strain at a high temperature (50 ° C.) is small (0.1%) and G ′ when the strain is large (10%). It was judged that the smaller the ΔG ′, the better the dispersibility of the filler.

(5) Abrasion resistance Abrasion resistance was measured by using “Aklon Rubber Abrasion Tester” manufactured by Yasuda Seiki Seisakusho and according to JIS K6264-2, test method A, load 44.1N, and the amount of wear at 3000 rotations. . In Table 3, evaluation was made with an index of Comparative Example 4 and Table 4 with Comparative Example 5 being 100. It was judged that the higher the index, the smaller the amount of wear and the better the wear resistance.

  As shown in Tables 3 and 4, it was confirmed that each example was excellent in fuel economy, filler dispersibility, and abrasion resistance. On the other hand, it was confirmed that each comparative example was inferior in at least one of fuel economy, filler dispersibility, and wear resistance.

  The modified conjugated diene polymer obtained by the production method of the present invention can be used as a raw material rubber for tires, and the rubber composition containing the same can be used as a member for tire treads, sidewalls and other tires. It can also be used as a raw material for various seals including hoses, belts, shoe soles and windows, vibration damping rubber and other industrial products.

Claims (6)

Using a lanthanum series metal compound as an initiator, polymerizing a conjugated diene monomer to obtain a conjugated diene polymer;
And the conjugated diene polymer, and reacting the amino group-containing compound represented by the following following formula (1),
A process for producing a modified conjugated diene-based polymer.
(In Formula (1), R < ¹ > -R < ⁴ > represents a C1-C20 alkyl group or an aryl group each independently, R < ⁵ > and R < ⁶ > represent a C1-C20 alkylene group, R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.) Using a lanthanum series metal compound as an initiator, polymerizing a conjugated diene monomer to obtain a conjugated diene polymer;
And the conjugated diene polymer, and obtaining a reacting the amino group-containing compound represented by the following following formula (1) the modified conjugated diene polymer,
A step of blending 100 parts by mass of a rubber component containing 10 parts by mass or more of the modified conjugated diene polymer and 0.5 to 300 parts by mass of a silica-based inorganic filler;
A process for producing a modified conjugated diene polymer composition having
(In Formula (1), R < ¹ > -R < ⁴ > represents a C1-C20 alkyl group or an aryl group each independently, R < ⁵ > and R < ⁶ > represent a C1-C20 alkylene group, R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.) Using a lanthanum series metal compound as an initiator, polymerizing a conjugated diene monomer to obtain a conjugated diene polymer;
And the conjugated diene polymer, and obtaining a reacting the amino group-containing compound represented by the following following formula (1) the modified conjugated diene polymer,
A step of obtaining a modified conjugated diene polymer composition by blending 100 parts by mass of a rubber component containing 10 parts by mass or more of the modified conjugated diene polymer and 0.5 to 300 parts by mass of a silica-based inorganic filler. When,
Vulcanizing the modified conjugated diene polymer composition;
The manufacturing method of the tire which has this.
(In Formula (1), R < ¹ > -R < ⁴ > represents a C1-C20 alkyl group or an aryl group each independently, R < ⁵ > and R < ⁶ > represent a C1-C20 alkylene group, R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.) A modified conjugated diene polymer to which an amino group-containing compound represented by the following formula (1) is bonded,
A modified conjugated diene polymer having a 1,4-bond amount of 80% or more.
(In Formula (1), R < ¹ > -R < ⁴ > represents a C1-C20 alkyl group or an aryl group each independently, R < ⁵ > and R < ⁶ > represent a C1-C20 alkylene group, R ⁷ represents Si, O, or N, and represents a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with an organic group having no active hydrogen, and m is an integer of 1 to 3. And n is an integer of 1 to 3.) 100 parts by mass of a rubber component containing 10 parts by mass or more of the modified conjugated diene polymer according to claim 4,
0.5 to 300 parts by mass of a silica-based inorganic filler,
A modified conjugated diene polymer composition comprising:   A tire comprising the modified conjugated diene polymer composition according to claim 5.