JP5688313B2 - Rubber composition and tire - Google Patents

Description

  The present invention relates to a rubber composition capable of establishing low heat build-up, wear resistance, and storage elastic modulus, and a tire using the rubber composition.

  In recent years, demands for reducing the fuel consumption of automobiles are becoming more severe in connection with the movement of global carbon dioxide emission regulations due to the social demand for energy saving and the increasing interest in environmental problems. In order to meet such demands, a reduction in rolling resistance has also been demanded for tire performance. As a technique for reducing the rolling resistance of the tire, although a technique by optimizing the tire structure has been studied, the most common technique is to use a material having lower heat generation as the rubber composition.

  In order to obtain such a rubber composition having a low exothermic property, many technical developments have been made on modified rubbers for rubber compositions using silica or carbon black as a filler. Among them, a method of modifying the polymerization active terminal of a conjugated diene polymer obtained by anionic polymerization using organolithium with a tin compound and an alkoxysilane derivative containing a functional group that interacts with a filler is particularly effective. It has been proposed (see, for example, Patent Document 1).

Further, in order to further improve the modification effect, a method of adding a condensation accelerator to the reaction system in modifying the active terminal of the conjugated diene polymer with alkoxysilane has been proposed (for example, Patent Documents 2 and 3). ).
However, in these rubber compositions, although it was possible to improve the low heat buildup, it was difficult to simultaneously improve the wear resistance and the storage elastic modulus.

By the way, it is well known that coordination anionic polymerization using a catalyst system typified by a Ziegler-Natta catalyst can homopolymerize olefins and dienes. However, in such a polymerization reaction system, it has been difficult to efficiently copolymerize olefin and diene.
For example, Patent Document 4 discloses a conjugated diene polymerization catalyst containing a group IV transition metal compound of the periodic table having a cyclopentadiene ring structure. As a monomer copolymerizable with this conjugated diene, ethylene is disclosed. Etc. α-olefins are exemplified.
For example, Patent Document 5 discloses an olefin polymerization catalyst comprising a transition metal compound such as a titanium compound and a cocatalyst, and a copolymer of an α-olefin and a conjugated diene compound.

Patent Document 6 discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component. It is inserted into the copolymer in the form of -1,2-cyclohexane and has a structure different from that of the copolymer of the present invention.
Patent Document 7 discloses a butadiene polymer having a cis content of 92% and an ethylene content of 3% or 9%.
Further, Patent Document 8 discloses an unsaturated elastomer composition comprising an unsaturated olefin copolymer and rubber.
However, the inventions of Patent Documents 4 to 8 are intended to improve the heat resistance and ozone resistance of the rubber composition, and cannot improve the wear resistance and low heat build-up of the rubber composition. There wasn't.

Japanese Examined Patent Publication No. 6-57767 Japanese Patent Laid-Open No. 11-349632 International Publication No. 2003/087171 Pamphlet JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141 JP 2000-86857 A JP-A-11-228743

  The present inventor aims to provide a rubber composition capable of erecting low heat build-up, wear resistance and storage elastic modulus under such circumstances.

As a result of intensive studies to achieve the above object, the present inventors have found that the problem of the present invention can be solved by combining a modified conjugated diene polymer and a specific copolymer. The present invention has been completed.
That is, the present invention is a rubber composition comprising a modified conjugated diene polymer, a copolymer of a conjugated diene compound and a nonconjugated olefin, and a filler, and the modified conjugated diene polymer is A rubber composition having a functional group having an affinity for the filler in the chain and a tire using the rubber composition.

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which improves the low heat_generation | fever property, abrasion resistance, and a storage elastic modulus of a rubber composition can be provided.

It is sectional drawing of the tire radial direction and tread width direction of the tire which concerns on embodiment of this invention.

Hereinafter, the present invention will be described in detail. The rubber composition according to the present invention comprises a modified conjugated diene polymer in an amount of 3 to 97% by mass , and a conjugated diene compound having a conjugated diene ratio of 30 to 80% by mol and a non-conjugated olefin copolymer in an amount of 3 to 97% by mass. % of the rubber component 100 parts by mass comprising, a charging Hamazai rubber composition comprising 5 to 200 parts by weight, the modified conjugated diene polymer, affinity with the filler in the molecule chain It has the functional group which has property.
The rubber composition according to the present invention contains the modified conjugated diene polymer, a copolymer of a conjugated diene compound and a nonconjugated olefin, a rubber component other than a filler, a crosslinking agent, a vulcanization accelerator, and the like. May be.

<Copolymer of conjugated diene compound and non-conjugated olefin>
Next, a copolymer of a conjugated diene compound and a non-conjugated olefin will be described.
-Constitution of copolymer of conjugated diene compound and non-conjugated olefin Cis 1,4-bond of conjugated diene compound-derived portion (conjugated diene portion) of copolymer of conjugated diene compound and non-conjugated olefin used in the present invention The amount is preferably 25% or more, and preferably 50% or more. Furthermore, the cis 1,4-bond amount of the conjugated diene compound-derived moiety (conjugated diene moiety) is preferably more than 92%, more preferably 95% or more. If the cis-1,4 bond content of the conjugated diene compound part (part derived from the conjugated diene compound) is 25% or more, a low glass transition point (Tg) can be maintained. Physical properties such as wear are improved.

  By making the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) more than 92%, it becomes possible to improve crack growth resistance, weather resistance, and heat resistance. Moreover, when the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is 95% or more, the crack growth resistance, weather resistance, and heat resistance can be further improved.

  The amount of cis-1,4 bonds is the amount in the conjugated diene compound-derived moiety, and is not a ratio relative to the entire copolymer.

  The ratio of the conjugated diene compound in the copolymer of the conjugated diene compound and the non-conjugated olefin is preferably 30 mol% to 80 mol%. If the proportion of the conjugated diene compound is 30 mol% or more, the compatibility with the modified conjugated diene rubber or other diene rubber is better, and if it is 80 mol% or less, the proportion of non-conjugated olefin increases. It is preferable because the effects of maintaining a high elastic modulus and wear resistance can be more suitably enjoyed.

  The non-conjugated olefin is preferably an acyclic olefin. Moreover, it is preferable that carbon number of a nonconjugated olefin is a 2-10 alpha olefin. Since the α-olefin has a double bond at the α-position of the olefin, it can be efficiently copolymerized with the conjugated diene compound. Accordingly, preferred examples of non-conjugated olefins include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and among these, ethylene, propylene and 1-butene is preferred and ethylene is more preferred. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  The conjugated diene compound preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  The copolymer of the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  The copolymer of the conjugated diene compound and the non-conjugated olefin does not cause a problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a polymer structural material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer of the conjugated diene compound and the nonconjugated olefin is preferably 10,000 to 10,000,000. 1,000,000 is more preferable, and 50,000-600,000 is still more preferable. If Mw exceeds 10,000,000, the moldability may be deteriorated.

  The copolymer according to the present invention preferably has a conjugated diene compound-derived portion having a 1,2-adduct portion (including 3,4-adduct portion) content of 5% or less in the conjugated diene compound-derived portion. More preferably, it is 3% or less, More preferably, it is 2.5% or less.

  When the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is 5% or less, the weather resistance and ozone resistance of the copolymer according to the present invention are improved. Further improvement can be achieved. Furthermore, when the content of 1,2 adducts (including 3,4 adducts) in the conjugated diene compound portion is 2.5% or less, the copolymer of the present invention further improves ozone resistance and fatigue resistance. Can be improved.

  The content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

  Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 15 or less, and more preferably 10 or less. This is because if the molecular weight distribution exceeds 15, the physical properties may not be uniform.

  Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The copolymer of the conjugated diene compound and the non-conjugated olefin according to the present invention may be a random copolymer or a block copolymer. Alternatively, a taper copolymer may be used. The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, from a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. And at least one block portion (also referred to as a block structure) and a random portion (also referred to as a random structure) in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. It is a copolymer.
That is, the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously. Here, it is preferable that the chain structure of the non-conjugated olefin component does not contain many long-chain (high molecular weight) non-conjugated olefin block components but contains many short-chain (low molecular weight) non-conjugated olefin block components.

The structure of the block copolymer is (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of non-conjugated olefin monomer units. And B is a block part composed of monomer units of a conjugated diene compound, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multiblock copolymer.

When the copolymer of the conjugated diene compound and the non-conjugated olefin is a block copolymer, the block portion composed of the monomer units of the non-conjugated olefin exhibits static crystallinity. The above-mentioned modified conjugated diene polymer is complemented with a block copolymer of a conjugated diene compound and a nonconjugated olefin, so that the storage elastic modulus (G ′) of the modified conjugated diene polymer is obtained by the block portion exhibiting crystallinity. Can be suppressed.
Therefore, in the present invention, the copolymer of the conjugated diene compound and the non-conjugated olefin is preferably at least one selected from a block copolymer and a tapered copolymer.
Therefore, in the present invention, the copolymer is preferably at least one selected from a block copolymer and a taper copolymer.

-Manufacturing method of the copolymer of a conjugated diene compound and a nonconjugated olefin Next, the manufacturing method of the copolymer based on this invention is demonstrated in detail. However, the manufacturing method described in detail below is merely an example. The copolymer according to the present invention can polymerize a conjugated diene compound and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition.

  In the method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin, a normal coordination ion polymerization catalyst is used except that a polymerization catalyst described later, or first, second, and third polymerization catalyst compositions are used. Polymerization can be carried out in the same manner as in the method for producing a polymer. The polymerization catalyst or polymerization catalyst composition used in the present invention will be described later.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inert in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  A method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin includes, for example, (1) a polymerization catalyst composition in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The component of the product may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mol with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

  Moreover, in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the production method according to the present invention, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.

  In the production method according to the present invention, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Moreover, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches a peak, and therefore the pressure of the non-conjugated olefin is preferably 10 MPa or less.

  In the copolymer production method, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / L) and the concentration of the non-conjugated olefin (Mol / L) preferably satisfies the relationship of the following formula. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7

  According to the production method of the present invention, a conjugated diene compound that is a monomer is used in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. And non-conjugated olefin can be copolymerized.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式（ＩＩＩ）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物（以下、第一重合触媒組成物ともいう）が挙げられる。 -1st polymerization catalyst composition Next, the 1st polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As the first polymerization catalyst composition, the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The first polymerization catalyst composition may further contain other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene complex. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal. In particular, a metallocene complex having one cyclopentadienyl or a derivative thereof bonded to a central metal may be referred to as a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid-based metalloids include germyl Ge, stannyl Sn, and silyl Si. The metalloid group preferably has a hydrocarbyl group. The hydrocarbyl group possessed by the metalloid group is the same as the above hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

In the half metallocene cation complex represented by the above general formula (III), Cp ^R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^R 'having a cyclopentadienyl ring as a basic skeleton include the following.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）
一般式（ＩＩＩ）において、上記インデニル環を基本骨格とするＣｐ^R’は、一般式（Ｉ）のＣｐ^Rと同様に定義される。好ましい例も同様である。

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I). The preferable example is also the same.

In the general formula (III), Cp ^R ′ having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid-based metalloids include germyl Ge, stannyl Sn, and silyl Si. Moreover, it is preferable that a metalloid group has a hydrocarbyl group, and the hydrocarbyl group which a metalloid group has is the same as said hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formulas (I), (II) and (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio-n-butoxy group, a thioisobutoxy group, a thio-sec-butoxy group, and a thio-tert-butoxy group. An aliphatic thiolate group such as thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl- Arylthiolate groups such as 6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group Among these, among these, 2,4,6-triisopropylthiopheno Shi group is preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

  The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

（式中、Ｘ”はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすれば良いので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いれば良い。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。

（式中、Ｘ”はハライドを示す。）
上記一般式（ＩＩＩ）で表されるハーフメタロセンカチオン錯体は、例えば、次の反応により得ることができる。

ここで、一般式（ＩＶ）で表される化合物において、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、それぞれ独立して無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。また、一般式［Ａ］⁺［Ｂ］^-で表されるイオン性化合物において、［Ａ］⁺は、カチオンを示し、［Ｂ］^-は、非配位性アニオンを示す。

(In the formula, X ″ represents a halide.)
The metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

(In the formula, X ″ represents a halide.)
The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^R ′ represents each independently an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. The ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol based on the metallocene complex. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 2-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  Further, in the first polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are respectively suitable cocatalysts. In combination, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

-2nd polymerization catalyst composition Next, the 2nd polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can be preferably mentioned.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the second polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). Including.

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (A) and the component (B), and the polymerization catalyst composition is the ionic compound (B). -1) and at least one of the above halogen compounds (B-3),
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). It is necessary to include.
Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. The second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition.

  The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the rare earth element compound and a reaction product of the rare earth element compound and a Lewis base are used. Does not have a bond between rare earth elements and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂ · L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (XII)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio-n-butoxy group, thioisobutoxy group, An aliphatic thiolate group such as a thio-sec-butoxy group or a thio-tert-butoxy group; Ofenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-ter -Arylamide groups such as butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilyl such as bistrimethylsilylamide group Amide group; silyl group such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, And halogen atoms such as iodine atom. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade names made by Shell Chemical Co., Ltd., a mixture of isomers of C10 monocarboxylic acid Synthetic acids composed of products], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Residues of thiocarboxylic acids such as acids, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, phosphoric acid Dilauryl, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphate (1-methyl) Phosphoric acid ester such as heptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl) 2-ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphonate mono-2-ethylhexyl, 2-ethylhexylphosphonate mono-p-nonylphenyl, phosphonate mono-2- Residues of phosphonates such as ethylhexyl, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid , Dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2 -Ethylhe Xylyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid, etc. Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A) used in the second polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L ¹¹ is the same or different. May be.

  The component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that content of the sum total of (B) component in said 2nd polymerization catalyst composition is 0.1-50 times mole with respect to (A) component.

  The ionic compound represented by the above (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or its Lewis base as the component (A) to be cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarboundecaborate and the like can be mentioned. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Accordingly, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, it is preferable that it is 0.1-10 times mole with respect to (A) component, and, as for content of the ionic compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 1 time mole.

  The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, the repetition represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid 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 Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

-Polymerization catalyst Next, the polymerization catalyst used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As a polymerization catalyst, it is for superposition | polymerization with a conjugated diene compound and a nonconjugated olefin, and following formula (A):
R _a MX _b QY _b (A)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2).

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a及びＲ^bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^a及びＲ^bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^c及びＲ^dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、共役ジエン化合物と非共役オレフィンとの共重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、共重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 In a preferred example of the metallocene composite catalyst, the following formula (XV):

( ^Wherein M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 1 to 20 carbon atoms. R ^a and R ^b are μ-coordinated to M ¹ and Al, and R ^c and R ^d each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (XV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^R 's in the formula (XV) may be the same as or different from each other.

In the above formula (XV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R are coordinated μ to M ¹及A ^l. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすれば良いので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いれば良い。なお、上記メタロセン系複合触媒の構造は、¹Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 The metallocene composite catalyst is, for example, in a solvent in the following formula (XVI):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XVI), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (XV). In the above formula (XVI), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the catalyst can be easily synthesized. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or a multimer higher than that.

On the other hand, the organoaluminum compound used to produce the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. The amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mol, and more preferably about 10 times mol to the metallocene complex.

-3rd polymerization catalyst composition Next, the 3rd polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
The third polymerization catalyst composition is characterized in that it contains the above metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the above metallocene composite catalyst, it is possible to arbitrarily control the content of each monomer component in the copolymer. It becomes.

  In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compound composed of a boron anion and a cation is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol based on the metallocene composite catalyst.

  In the third polymerization catalyst composition, it is necessary to use the metallocene composite catalyst and the boron anion, but a reaction system for reacting the metallocene catalyst represented by the formula (XVI) with an organoaluminum compound. If a boron anion is present, the metallocene composite catalyst of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. In addition, these aluminoxanes may be used individually by 1 type, and may be used in combination of 2 or more type.

<Modified conjugated diene polymer>
The modified conjugated diene polymer according to the present invention has a functional group having an affinity for the filler in the molecular chain, and may have the functional group at the end of the molecular chain. You may have in the principal chain or side chain of the molecular chain. When the modified conjugated diene polymer has the functional group at the molecular chain end, the modified conjugated diene polymer has the functional group at the polymerization initiation end of the modified conjugated diene polymer, and the polymerization of the modified conjugated diene polymer. And having the functional group at the active end (polymerization end). What is necessary is just to have this functional group in at least one of a polymerization start terminal and a polymerization active terminal (polymerization terminal).

The modified conjugated diene polymer according to the present invention is obtained by anionic polymerization or coordination polymerization.
As the coordination polymerization type polymer, those based on the catalyst composition disclosed in JP-A Nos. 06-211916, 08-073515, 10-306113, 11-035633, Japanese Patent No. 3724125, Japanese Patent No. 4489194 and the like are preferable. Moreover, the modified high cis-1,4-polybutadiene rubber (modified high cis-1,4-BR) described in JP-T-2003-514078 is suitably used in the present invention.

The modified conjugated diene polymer according to the present invention preferably contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group.
This is because these functional groups are rich in reactivity with the reinforcing filler and improve the reinforcing property of the rubber composition. In particular, a tin-containing functional group is preferable because it has high reactivity with carbon black. A silicon-containing functional group is preferable because of its high reactivity with silica. Nitrogen-containing functional groups are preferred because they are highly reactive with both carbon black and silica.

The functional group in the modified conjugated diene polymer is a tin compound, a lithium amide compound, a hydrocarbyloxysilane compound represented by the following general formula (1), a hydrocarbyloxysilane compound represented by the following general formula (2), And a residue of a compound selected from the group consisting of partial condensates of these hydrocarbyloxysilane compounds.
The above residues are formed by leaving one or more hydrocarbyloxy groups of the hydrocarbyloxysilane compound and its partial condensate.

In the general formula (1), n1 + n2 + n3 + n4 = 4 (where n2 is an integer of 1 to 4, n1, n3 and n4 are integers of 0 to 3), and A ¹ is a saturated cyclic tertiary amine Compound residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester group, carbonic acid dihydrocarbyl ester group, nitrile group, Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester group, metal salt of (thio) carboxylic acid ester, carboxylic acid anhydride residue, carboxylic acid halogen compound residue, And at least one functional group selected from a primary or secondary amino group or a mercapto group protected with a hydrolyzable group, and n4 is 2 or more. Well be the same or different when, R ¹ is a monovalent organic group, preferably a monovalent C6-18 aliphatic or or alicyclic hydrocarbon group having a carbon monovalent C20 And when n1 is 2 or more, they may be the same or different, and R ³ is a monovalent organic group or a halogen atom, and the monovalent organic group preferably has 1 carbon atom. -20 monovalent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when n3 is 2 or more, they may be the same or different, R ² is a monovalent organic group, preferably a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a nitrogen-containing organic group. , When n2 is 2 or more, they are the same or different from each other, or together form a ring R ⁴ is a divalent organic group, preferably a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, When n4 is 2 or more, they may be the same or different.

In the general formula (2), p1 + p2 + p3 = 2 (where p2 is an integer of 1 to 2, p1 and p3 are integers of 0 to 1), and A ² is NR ^a (R ^a is A monovalent hydrocarbon group, a hydrolyzable group or a nitrogen-containing organic group), or sulfur, and R ⁵ is a monovalent organic group, preferably a monovalent aliphatic or fatty acid having 1 to 20 carbon atoms. A cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁷ is preferably a monovalent organic group, a halogen atom or a monovalent organic group, preferably having 1 to 20 carbon atoms. A valent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁶ is a monovalent organic group, preferably a monovalent fatty acid having 1 to 20 carbon atoms. An aliphatic or alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group, and p2 is 2. In some cases, they are the same or different from each other, or together form a ring, and R ⁸ is a divalent organic group, preferably a divalent aliphatic or alicyclic hydrocarbon having 1 to 20 carbon atoms. Or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

  Examples of tin-containing functional groups include tin halide compound residues, such as triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltin. Preference is given to residues which are produced by leaving one or more chlorine atoms from a tin chloride compound selected from the group consisting of dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride and tin tetrachloride.

A residue from which lithium is released from a lithium amide compound described later as an initiator for anionic polymerization is also preferable as the nitrogen-containing functional group contained in the modified conjugated diene polymer.
By using a lithium amide compound as a polymerization initiator, a functional group having an affinity for the filler is introduced into the polymerization initiation terminal of the conjugated diene polymer to obtain a modified conjugated diene polymer.

The silicon-containing functional group and the nitrogen-containing functional group are selected from the group consisting of a hydrocarbyloxysilane compound represented by the above general formula (1) and a hydrocarbyloxysilane compound represented by the following general formula (2). It is preferably a residue of a compound.
Furthermore, the hydrocarbyloxysilane compound represented by the general formula (1) is more preferably a hydrocarbyloxysilane compound represented by the following general formulas (3) to (6).

In the general formula (3), q1 + q2 = 3 (where q1 is an integer of 0 to 2 and q2 is an integer of 1 to 3), R ¹¹ is a divalent organic group, preferably 1 carbon atom. A divalent aliphatic or alicyclic hydrocarbon group of ˜20 or a divalent aromatic hydrocarbon group of 6 to 18 carbon atoms, wherein R ¹² and R ¹³ are each independently a monovalent organic group, preferably Is a trimethylsilyl group, a tert-butyldimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, R ¹² and R ¹³ Is a divalent organic group that forms a cyclic group together with R ¹¹ , or a divalent organic group that forms a cyclic group together with R ^11, and R ¹⁴ is a monovalent organic group, preferably carbon. A monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic having 6 to 18 carbon atoms Hydrocarbon is a group may be the same or different in the case of q1 is 2, R ¹⁵ is a monovalent organic group, preferably an aliphatic or alicyclic monovalent hydrocarbon group having 1 to 20 carbon atoms Alternatively, it is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when q2 is 2 or more. The divalent organic group forming the cyclic group is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Is preferred.

In the general formula (4), R ¹⁶ is a divalent organic group or a single bond, and R ¹⁷ is a divalent organic group or a trivalent organic group that forms a cyclic group together with R ¹⁸ or R ^19. R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a monovalent organic group, or a divalent organic group in which R ¹⁸ and R ¹⁹ together form a cyclic group, or R ^{18 17} is a divalent organic group which forms a cyclic group together with R ¹⁷ , R ²⁰ and R ²¹ are each independently a monovalent organic group, and r1 + r2 = 3 (where r1 is an integer of 0-2) And r2 is an integer of 1 to 3.), the plurality of R ²⁰ may be the same or different, and the plurality of R ²¹ may be the same or different. . Among the above, the monovalent organic group is preferably a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The organic group is preferably a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and a trivalent organic group is preferably A trivalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a trivalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R ¹⁷ is preferably bonded to the nitrogen of the imine through a carbon atom. Note that R ¹⁶ is a single bond means that Si and R ¹⁷ are directly bonded by a single bond.

In the general formula (5), R ²² is a divalent organic group or a single bond, and R ²³ is a divalent organic group or a group formed together with R ²⁴ , R ²⁵ or R ²⁶ to form a cyclic group. the valence of the organic radical, or R ²⁵ and R ²⁶ is a divalent organic group each independently a hydrogen atom, and a and R ²⁶ organic group or R ²⁵ monovalent form a cyclic group together Or a divalent organic group which forms a cyclic group together with R ²⁴ , R ²⁷ and R ²⁸ are each independently a monovalent organic group, and s1 + s2 = 3 (where s1 is 0 to 0) 2 is an integer of 2 and s2 is an integer of 1 to 3.), a plurality of R ²⁷ may be the same or different, and a plurality of R ²⁸ may be the same or different. May be. Among the above, the monovalent organic group is preferably a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The organic group is preferably a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and a trivalent organic group is preferably A trivalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a trivalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

In the general formula (6), E is an oxygen atom or a sulfur atom, R ³¹ is a divalent organic group or a single bond, R ³² is a divalent organic group, and R ³³ and R ³⁴ are respectively Independently a monovalent organic group, t1 + t2 = 3 (where t1 is an integer from 0 to 2 and t2 is an integer from 1 to 3), and the plurality of R ³³ may be the same. They may be different, and the plurality of R ³⁴ may be the same or different. Among the above, the monovalent organic group is preferably a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The organic group is preferably a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

In the general formulas (1) to (6), R ⁴ , R ⁸ , R ¹¹ , R ¹⁶ , R ^22, and R ³¹ can each independently preferably represent an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched, or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.

In the general formulas (1) to (6), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³³ and R ³⁴ are each independently a monovalent organic group, an alkyl group having 1 to 20 carbon atoms, or a group having 2 to 18 carbon atoms. Examples thereof include an alkenyl group, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. Here, the alkyl group and alkenyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl, hexenyl, octenyl Group, cyclopentenyl group, cyclohexenyl group and the like.
The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Further, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
R ¹² and R ¹³ may be the same as the above-mentioned R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ , R ¹⁸ and R ¹⁹ , but a hydrolyzable group It is particularly preferred that Here, as the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.

In the general formulas (4) to (6), when R ¹⁷ , R ^23, and R ³² are divalent organic groups, each independently preferably represents an alkylene group having 1 to 20 carbon atoms. . The alkylene group may be linear, branched, or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group. When R ¹⁷ and R ²³ are trivalent organic groups, an alkylidine group having 1 to 20 carbon atoms can be preferably exemplified.

In the general formula (4), R ¹⁸ and R ¹⁹ together form a divalent organic group that forms a cyclic group, and R ¹⁸ or R ¹⁹ forms a cyclic group together with R ^17. Or a divalent organic group in which R ²⁵ and R ²⁶ together form a cyclic group, or R ²⁵ or R ²⁶ together with R ^{24 in the} general formula (5) As the divalent organic group forming the group, an alkylene group having 1 to 20 carbon atoms can be preferably exemplified.

  Of the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) ) -3- (Triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene)- 3- (Triethoxysilyl) -1-propanamine and trimethoxysilyl corresponding to these triethoxysilyl compounds Preferred examples include compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, and ethyldimethoxysilyl compounds. Among these, N- (1-methylpropylidene) -3- ( Triethoxysilyl) -1-propanamine and N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine are more preferable and are represented by the above general formula (4). N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, which is a hydrocarbyloxysilane compound, is particularly suitable.

  Other imine residue (amidine group) -containing compounds include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4. , 5-dihydroimidazole, 3- [10- (triethoxysilyl) decyl] -4-oxazoline, among which 3- (1-hexamethyleneimino) propyl (triethoxy) silane, (1-Hexamethyleneimino) methyl (trimethoxy) silane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (trimethoxysilyl) propyl] -4,5- A preferred example is dihydroimidazole. N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl)- 4,5-dihydroimidazole and the like can be mentioned, among which N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

  Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), the isocyanate group-containing compounds include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyl. Examples thereof include methyldiethoxysilane and 3-isocyanatopropyltriisopropoxysilane. Among these, 3-isocyanatopropyltriethoxysilane is preferable.

  Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), examples of the cyclic tertiary amino group-containing compound include 3- (1-hexamethyleneimino) propyl (triethoxy) silane and 3- (1-hexamethylene). Imino) propyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (triethoxy) silane, 2 -(1-Hexamethyleneimino) ethyl (trimethoxy) silane, 3- (1-pyrrolidinyl) propyl (triethoxy) silane, 3- (1-pyrrolidinyl) propyl (trimethoxy) silane, 3- (1-heptamethyleneimino) propyl (Triethoxy) silane, 3- (1-do Kamechiren'imino) propyl (triethoxy) silane, 3- (1-hexamethyleneimino) propyl (diethoxy) methylsilane, 3- (1-hexamethyleneimino) can be preferably exemplified propyl (diethoxy) ethylsilane. Particularly preferred are 3- (1-hexamethyleneimino) propyl (triethoxy) silane and (1-hexamethyleneimino) methyl (trimethoxy) silane. Furthermore, examples of other hydrocarbyloxysilane compounds include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 4-ethylpyridine and the like.

Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), 3-dimethylaminopropyl (triethoxy) silane and 3-dimethylaminopropyl (trimethoxy) silane are used as the acyclic tertiary amino group-containing hydrocarbyloxysilane compounds. 3-diethylaminopropyl (triethoxy) silane, 3-diethylaminopropyl (trimethoxy) silane, 2-dimethylaminoethyl (triethoxy) silane, 2-dimethylaminoethyl (trimethoxy) silane, 3-dimethylaminopropyl (diethoxy) methylsilane, 3 -Dibutylaminopropyl (triethoxy) silane and the like, among which 3-diethylaminopropyl (triethoxy) silane and 3-dimethylaminopropyl (triethoxy) ) Silanes are preferred.
Further, examples of the nitrogen-containing hydrocarbyloxysilane compound represented by the general formula (1) include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 2-cyanoethyltriethoxysilane and the like. It is done.

Of the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (3), a compound in which both R ¹² and R ¹³ are hydrolyzable groups (particularly trimethylsilyl group), that is, a hydrolyzable primary amino group. Are preferred, such as N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) amino. Particularly preferred are ethylmethyldimethoxysilane and N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane.
One of R ¹² and R ¹³ is a hydrolyzable group, and the other is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Hydrocarbyloxysilane compounds that are groups, i.e., wherein the secondary amino group is protected with a hydrolyzable group are also preferred, such as N-trimethylsilyl (methyl) aminopropylmethyldimethoxysilane, N-trimethylsilyl (ethyl) aminopropylmethyldimethoxysilane, N-trimethylsilyl (methyl) aminopropylmethyldiethoxysilane, N-trimethylsilyl (ethyl) aminopropylmethyldiethoxysilane, N-trimethylsilyl (methyl) aminoethylmethyldimethoxysilane, N-trimethylsilyl (ethyl) aminoethylmethyldimethoxysilane, N-trimethylsilyl Methyl) aminoethyl methyl diethoxy silane, N- trimethylsilyl (ethyl) amino ethyl methyl diethoxy silane, and the like 1-trimethylsilyl-2-ethoxymethyl-1-aza-2-silacyclopentane are particularly preferred.

  Examples of the epoxy group-containing hydrocarbyloxysilane compound represented by the general formula (5) include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacrylic acid 3- (Trimethoxysilyl) propyl, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltriphenoxysilane, (2- (3,4-epoxycyclohexyl) ethyl) methyldimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyl) methyldiethoxysilane, 2- (3,4-epoxy Rohexyl) ethyl) ethyldiethoxysilane, (2- (3,4-epoxycyclohexyl) ethyl) methyldiphenoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3- Examples thereof include glycidoxypropyltriphenoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) ethyldiethoxysilane, and (3-glycidoxypropyl) methyldiphenoxysilane.

  Examples of the (thio) isocyanate-containing hydrocarbyloxysilane compound represented by the general formula (6) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltriisopropoxysilane, 3-isocyanatopropyltriphenoxysilane, (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane, (3-isocyanatopropyl) ethyldiethoxysilane, (3-isocyanatopropyl) ) Methyldiphenoxysilane and the like.

As the nitrogen-containing functional group of the modified conjugated diene polymer in the present invention, one or more of —OR ^{3 of the} hydrocarbyloxysilane compound represented by the above general formulas (1) to (4) and its partial condensate is released. Among the residues formed in this manner, the residue having the primary amino group or the secondary amino group obtained by leaving the hydrolyzable group of the primary amino group or the secondary amino group protected by the hydrolyzable group is removed. Groups are preferred. This is because the primary amino group or the secondary amino group particularly improves the reinforcing properties of both carbon black and silica. Since these residues are highly reactive with the reinforcing filler, the reaction between the modified conjugated diene polymer and the reinforcing filler further improves the reinforcing property of the rubber composition, and the dry steering stability performance, This is because the wear resistance and fracture resistance are further improved. From this viewpoint, a residue having a primary amino group is particularly preferable.

In the rubber composition of the present invention, the modified conjugated diene polymer is preferably a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
Examples of the conjugated diene monomer used in the modified conjugated diene polymer include 1.3-butadiene, isoprene, 1.3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1, and the like. Examples include 3-butadiene and 1,3-hexadiene. These may be used alone or in combination of two or more, and among these, 1,3-butadiene is particularly preferable.
Examples of the aromatic vinyl monomer used in the modified conjugated diene polymer include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexyl. Examples thereof include styrene and 2,4,6-trimethylstyrene. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.
The content of the aromatic vinyl structure in the modified conjugated diene polymer is not particularly limited, but is preferably 0 to 50% by weight, and more preferably 0 to 40% by weight.

  The conjugated diene polymer having an active terminal used in the method of the present invention is obtained by copolymerizing a diene monomer alone or with another monomer, and the production method is not particularly limited. Any of a solution polymerization method, a gas phase polymerization method and a bulk polymerization method can be used, but a solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.

The active site metal present in the molecule of the conjugated diene polymer is preferably one selected from alkali metals and alkaline earth metals, preferably alkali metals, and particularly preferably lithium metal.
In the solution polymerization method, for example, an organic alkali metal compound, particularly a lithium compound is used as a polymerization initiator, and a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound are anionically polymerized to produce a target polymer. Can do.

  The lithium compound of the polymerization initiator is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal. A conjugated diene polymer having a polymerization active site is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.

  As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl. Examples include lithium, phenyllithium, 2-naphthyllithium, 2-butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, cyclobenchyllithium, and reactive organisms of diisopropenylbenzene and butyllithium. Of these, n-butyllithium is particularly preferred.

On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, lithium di Heptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, in view of the interaction effect on carbon black and the ability to initiate polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable, In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.
In general, these lithium amide compounds prepared in advance from a secondary amine and a lithium compound can be used for polymerization, but they can also be prepared in-situ. The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound are The desired conjugated diene polymer can be obtained by anionic polymerization in the presence of the randomizer used, if desired, using a lithium compound as a polymerization initiator.

  The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

Specific examples of randomizers used as desired include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N -Ethers such as methylmorpholine, N, N, N ', N'-tetramethylethylenediamine, 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
Those skilled in the art are able to control the content of the vinyl structure contained in the polymer obtained by using an appropriate amount of these randomizers when producing a polymer using 1,3-butadiene as a monomer. Is known to. When the lithium compound is used as a polymerization initiator, the content of the vinyl structure contained in the modified conjugated diene polymer used in the present invention is not particularly limited, but is preferably between 10% by weight and 70% by weight, and 15% by weight. More preferred is between% and 60% by weight.

  The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

In the present invention, the tin compound or the hydrocarbyloxysilane compound represented by the above general formulas (1) to (6) at the active end of the conjugated diene polymer obtained as described above (hereinafter, A denaturing reaction is performed in which a “denaturing agent” is sometimes reacted.
In the modification reaction with the above modifier, the amount of the modifier used is preferably 0.5 to 200 mmol / kg · conjugated diene polymer. The content is more preferably 1 to 100 mmol / kg · conjugated diene polymer, and particularly preferably 2 to 50 mmol / kg · conjugated diene polymer. Here, the conjugated diene polymer means the mass of only a polymer not containing an additive such as an anti-aging agent added at the time of production or after production. By making the usage-amount of a modifier into the said range, it is excellent in the dispersibility of a filler, and the mechanical property after vulcanization | cure, abrasion resistance, and low exothermic property are improved.
The method for adding the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, and a continuous addition method. preferable.
Further, the modifier may be bonded to any of the polymerization initiation terminal, the polymerization termination terminal, the polymer main chain, and the side chain, but it can suppress the loss of energy from the polymer terminal and improve the low exothermic property. Therefore, it is preferably introduced at the polymerization initiation terminal or the polymerization termination terminal.

In the present invention, after the above modification reaction, if desired, a condensation reaction may be further performed using a specific condensation accelerator.
The condensation accelerator used in the present invention is composed of a compound of an element belonging to at least one of groups 4A, 2B, 3B and 5B in the periodic table.
Specifically, the condensation accelerator is composed of a compound of zirconium (Zr), bismuth (Bi), aluminum (Al), or titanium (Ti). An acid salt or an acetylacetonate complex salt is preferable, and among them, at least one selected from the following (a) to (g) is preferable.
(A); bismuth carboxylate, (b); zirconium alkoxide, (c); zirconium carboxylate, (d); aluminum alkoxide, (e); aluminum carboxylate (f); titanium (G); titanium alkoxide

  Specific condensation accelerators include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, tris (linoleate) bismuth. , Tetraethoxyzirconium, tetra n-propoxyzirconium, tetra i-propoxyzirconium, tetra n-butoxyzirconium, tetrasec-butoxyzirconium, tetratert-butoxyzirconium, tetra (2-ethylhexyl) zirconium, zirconium tributoxyzirate, zirconium Tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium Xyacetylacetonate bis (ethylacetoacetate), zirconium tetrakis (acetylacetonate), zirconium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, bis (Naphthate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexanoate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthate) zirconium , Tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linole) ) Zirconium, triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, tri (2-ethylhexyl) aluminum, aluminum dibutoxy systemate Aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethylhexanoate) aluminum , Tris (laurate) aluminum, Tris (naphthate) aluminum, Tris (stearate) aluminum, Lith (oleate) aluminum, tris (linoleate) aluminum, and the like can be mentioned. Among these, tris (2-ethylhexanoate) bismuth, tetra n-propoxy zirconium, tetra n-butoxy zirconium, bis (2 -Ethylhexanoate) zirconium oxide, bis (oleate) zirconium oxide, tri-i-propoxyaluminum, trisec-butoxyaluminum, tris (2-ethylhexanoate) aluminum, tris (stearate) aluminum, zirconium tetrakis (acetyl) Acetonate), aluminum tris (acetylacetonate), tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) thio Tetrakis (2-propyl-1,3-hexanediolato) titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1, 3-pentanediolato) titanium, tetrakis (2-methyl-1,3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3- Pentanediolato) titanium, tetrakis (2-butyl-1,3-pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl-1,3-heptanediolato) titanium, tetrakis (2- Ethyl-1,3-heptanediolato) titanium, tetrakis (2-propyl-1,3-heptanediolato) thio Emissions, tetrakis (2-butyl-1,3 Heputanjiorato) titanium, tetrakis (2-ethylhexoxy) titanium, tetramethoxy titanium, etc. tetraethoxy titanium and the like.

The amount of the condensation accelerator used is preferably such that the number of moles of the compound is 0.1 to 10 as the molar ratio to the total amount of hydrocarbyloxy groups present in the reaction system, and 0.5 to 5 Particularly preferred. By setting the use amount of the condensation accelerator within the above range, the condensation reaction proceeds efficiently.
The condensation reaction in the present invention is preferably performed in an aqueous solution, and the temperature during the condensation reaction is preferably 85 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 110 to 150 ° C. By setting the temperature during the condensation reaction within the above range, the condensation reaction can be progressed and completed efficiently, and the deterioration of the quality due to the aging reaction of the polymer due to changes over time of the resulting modified conjugated diene polymer is suppressed. Can do.
The condensation reaction time is usually about 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly. Moreover, the pressure of the reaction system at the time of the condensation reaction is usually 0.01 to 20 MPa, preferably 0.05 to 10 MPa.
There is no restriction | limiting in particular about the form of a condensation reaction, You may carry out by a continuous type using apparatuses, such as a batch type reactor and a multistage continuous type reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.

<Filler>
The rubber composition can be blended with a filler capable of reinforcing the rubber composition (referred to as a reinforcing filler). Examples of the reinforcing filler include carbon black and inorganic filler. At least one selected from carbon black and inorganic filler is preferred.
There is no restriction | limiting in particular as an inorganic filler, According to the objective, it can select suitably. Examples of the inorganic filler include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples include potassium acid and barium sulfate. These may be used individually by 1 type and may use 2 or more types together. When an inorganic filler is used, a silane coupling agent may be used as appropriate. As the inorganic filler, silica is preferable, and as the filler, at least one selected from carbon black and silica is more preferable.

  There is no restriction | limiting in particular in content of a reinforcing filler, Although it can select suitably according to the objective, 5 mass parts-200 mass parts are preferable with respect to 100 mass parts of rubber components contained in a rubber composition. If the content of at least one of the reinforcing fillers is less than 5 parts by mass, the effect of reinforcing the rubber composition may not be sufficiently obtained. Moreover, when content of a reinforcing filler exceeds 200 mass parts, a reinforcing filler becomes difficult to disperse | distribute to the said rubber component, and the performance as a rubber composition may be reduced.

<Crosslinking agent>
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, and a sulfur compound. Of these, a sulfur-based crosslinking agent is more preferable as the tire rubber composition.
There is no restriction | limiting in particular as content of a crosslinking agent, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of rubber components. If the content of the crosslinking agent is less than 0.1 parts by mass, the crosslinking hardly proceeds, or if it exceeds 20 parts by mass, the crosslinking may tend to proceed during kneading with some crosslinking agents, or vulcanization may occur. The physical properties of the material may be impaired.

<Vulcanization accelerator>
As the vulcanization accelerator, compounds such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate and xanthate can be used. If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, scorch prevention agents, Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.

<Content of copolymer of conjugated diene compound and non-conjugated olefin>
There is no restriction | limiting in particular as content in the rubber component of the copolymer of a conjugated diene compound and a nonconjugated olefin, Although it can select suitably according to the objective, 3 mass% or more is preferable. When the content of the copolymer of the conjugated diene compound and the non-conjugated olefin in the rubber component is 3% by mass or more, the storage elastic modulus can be further increased.
Further, if the content of the modified diene polymer in the rubber component is 3% by mass or more, the low heat build-up and the wear resistance can be further improved, which is preferable.
From the above, in the rubber component of the rubber composition of the present invention, the copolymer of the conjugated diene compound and the nonconjugated olefin is preferably 3 to 97% by mass, and the modified diene polymer is 3 to 97% by mass. Preferably there is.

<Rubber components other than copolymer>
There is no restriction | limiting in particular as rubber components other than a copolymer, According to the objective, it can select suitably. For example, natural rubber, various butadiene rubber, various styrene-butadiene copolymer rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene -Propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber , Epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, and the like. These may be used individually by 1 type and may use 2 or more types together.

<Crosslinked rubber composition>
The crosslinked rubber composition according to the present invention is not particularly limited as long as it is obtained by crosslinking the rubber composition described above, and can be appropriately selected according to the purpose. The crosslinking conditions are not particularly limited and may be appropriately selected according to the purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.

<Tire>
Tire structure A tire 100 using the rubber composition according to the present invention will be described with reference to FIG. The tire 100 includes a pair of bead cores 111 and 112, stiffeners 113 and 114, and a carcass ply 121. The stiffeners 113 and 114 extend outward from the bead cores 111 and 112 in the tire radial direction. The carcass ply 121 is folded back at the bead cores 111 and 112 outward in the tread width direction of the stiffeners 113 and 114 to form a horseshoe-shaped tire case shape. On the outer side in the tire radial direction of the carcass ply 121, a belt portion 115 including a plurality of belt layers is disposed.
A tread portion 118 is disposed outside the belt portion 115 in the tire radial direction. In addition, an inner liner 130 is disposed as an air permeation preventive layer on the inner side in the tire radial direction of the carcass ply 121.

  The tire according to the present invention is not particularly limited as long as the rubber composition and the crosslinked rubber composition according to the present invention are used, and can be appropriately selected according to the purpose. Examples of the application site in the tire of the rubber composition or the crosslinked rubber composition according to the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, a bead filler, an inner liner, and the like. .

-Tire manufacturing method A conventional method can be used as a tire manufacturing method according to the present invention. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.

<Applications other than tires>
Besides the tire application, the rubber composition or the crosslinked rubber composition according to the present invention can be used for vibration-proof rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses, foams, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
First, a modified conjugated diene polymer blended with the rubber compositions of Examples and Comparative Examples and a copolymer of a conjugated diene compound and a nonconjugated olefin were produced. A production example will be described below.

<Evaluation of Modified Conjugated Diene Polymer and Unmodified Conjugated Diene Polymer>
The modified conjugated diene polymer and the unmodified conjugated diene polymer were measured and evaluated by the following methods.
(1) Weight average molecular weight (Mw) before modification
It measured using GPC [the Tosoh make, HLC-8220] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.
(2) Vinyl bond content Determined by the infrared method (Morello method).

<Evaluation of copolymer of conjugated diene compound and non-conjugated olefin>
About the copolymer of the conjugated diene compound and the nonconjugated olefin, the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and DSC curve were measured and evaluated by the following methods. In addition, the vertical axis | shaft of a DSC curve shows a heat flow rate.

(1) Microstructure (1,2-vinyl bond amount (Vi (%)), cis-1,4 bond amount)
The microstructure (1,2-vinyl bond amount) of the butadiene moiety in the copolymer was determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm) according to the 1,2-vinyl bond component (5.0 -5.1 ppm) and the overall ratio of butadiene bond components (5-5.6 ppm), and the microstructure of the butadiene moiety in the copolymer (cis-1,4 bond content) was determined by ¹³ C-NMR spectrum. (100 ° C., d-tetrachloroethane standard: 73.8 ppm) and cis-1,4 bonding component (26.5-27.5 ppm) and total butadiene bonding component (26.5-27.5 ppm + 31.5-32. 5 ppm).
(2) Content of ethylene The content (mol%) of the ethylene moiety in the copolymer was determined by the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm) as a whole of the ethylene-bonded component (28. 5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm).
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.
(4) DSC curve The differential scanning calorimetry (DSC) was performed based on JIS K7121-1987, the DSC curve was drawn, and the block polyethylene melting temperature (DSC peak temperature) was measured. In order to avoid the influence of impurities such as single polymer and catalyst residue, the measurement is performed by immersing the copolymer in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then using the dried rubber component as a sample. did.

<Production Example of Modified Conjugated Diene Polymer>
The following five types were prepared as modified conjugated diene polymers.
Modified conjugated diene polymer 1: tin-modified butadiene rubber In a pressure-resistant glass container having an inner volume of about 900 ml which has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydrofurylpropane 0 .015 mmol was injected as a cyclohexane solution, 0.80 mmol of n-butyllithium (BuLi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion was almost 100%. To this polymerization system, 0.125 mmol of tin tetrachloride was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, 0.5 ml of an isopropanol 5% solution of 2,6-di-t-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying according to a conventional method, thereby modifying the modified conjugated diene polymer. 1 was obtained. The weight average molecular weight (Mw) before modification was 347,000, and the vinyl bond content was 20%.

-Modified conjugated diene polymer 2: Hexamethyleneimide-modified butadiene rubber In a pressure-resistant glass container having an internal volume of about 900 milliliters that has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydro After injecting 0.015 mmol of furylpropane as a cyclohexane solution and adding 0.80 mmol of lithium hexamethyleneimide (HMILi) as a denaturing agent to this, it is 4.5 hours in a 50 ° C. hot water bath equipped with a stirrer. Polymerization was performed. The polymerization conversion rate was almost 100%. Thereafter, the reaction was stopped by adding 0.5 ml of a 5 mass% isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT), followed by drying according to a conventional method, whereby a modified conjugated diene was obtained. A polymer 2 was obtained. The weight average molecular weight (Mw) of the obtained polymer 2 was 229,000, and the vinyl bond content was 20%.

Modified conjugated diene polymer 3: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine-modified butadiene rubber Dry glass-substituted nitrogen-resistant pressure-resistant glass having an internal volume of about 900 ml Into a container, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 0.015 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution, and 0.80 mmol of n-butyllithium (BuLi) was added thereto, Polymerization was carried out in a 50 ° C. hot water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. Further, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, manufactured by Chisso Corporation, trade name “Syra Ace S340”) 0.55 mmol was added as an unmodified modifier. After that, a denaturation reaction was further performed for 30 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-tert-butyl-p-cresol was further added to terminate the polymerization, followed by drying according to a conventional method, whereby the modified conjugated diene polymer 3 was obtained. Obtained. The number average molecular weight (Mw) of the obtained polymer 3 was 315,000, and the vinyl bond content was 20%.

Modified conjugated diene polymer 4: N- (1,3-dimethylbutylidene) -3- (tri in the process for producing N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane-modified butadiene rubber polymer 3 Modified conjugated diene polymer 4 was obtained by using N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane instead of ethoxysilyl) -1-propanamine. The number average molecular weight (Mw) of the obtained polymer 4 was 261,000, and the vinyl bond content was 20%.

Unmodified conjugated diene-based polymer 1: Unmodified butadiene rubber In a pressure-resistant glass container having an inner volume of about 900 ml that has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydrofurylpropane 0.015 mmol was injected as a cyclohexane solution, 0.80 mmol of n-butyllithium (BuLi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. Thereafter, a methanol solution containing 1.5 g of 2,4-tert-butyl-p-cresol was added to terminate the polymerization, and further dried according to a conventional method to obtain an unmodified conjugated diene polymer 1. It was. The number average molecular weight (Mw) of the obtained unmodified conjugated diene polymer 1 was 218,000, and the vinyl bond content was 20%.

<Production example of copolymer A of conjugated diene compound and non-conjugated olefin>
After adding 150 ml of toluene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 14.5 μmol was placed in a glass container. , Triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 14.1 μmol and diisobutylaluminum hydride 0.87 mmol were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 14.1 μmol in terms of gadolinium was added to the monomer solution, and polymerization was carried out at 50 ° C. for 5 minutes. Thereafter, 20 ml of a toluene solution containing 3.05 g (0.056 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 15 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was reduced at a rate of 0.2 MPa / min, while 6.09 g (0. The operation of adding 40 ml of a toluene solution containing 113 mol) and then performing polymerization for another 30 minutes was repeated a total of 3 times. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol. And vacuum-dried at 70 ° C. to obtain a copolymer A (multi-block copolymer). The yield of the obtained copolymer A was 24.50 g.

  As the microstructure of the butadiene portion in the obtained copolymer A, the amount of cis 1,4-bond is 97% and the amount of 1,2-vinyl bond is 1.4%. The rate was 34 mol%. The weight average molecular weight Mw was 205,000, the molecular weight distribution Mw / Mn was 9.15, and the block polyethylene melting temperature (DSC peak temperature) was 121 ° C.

Examples 1-4 and Comparative Examples 1-3
The rubber compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared by changing the combination and blending ratio of the modified conjugated diene polymers 1 to 4 and the copolymer A described above, and had low heat buildup and storage elasticity. Rate and wear resistance were evaluated. Tables 1 to 4 show the combinations and blending ratios of modified conjugated diene polymers 1 to 4 and copolymer A in Examples 1 to 4 and Comparative Examples 1 to 3, and evaluation results of low heat build-up, storage elastic modulus, and wear resistance. Shown in

<Evaluation method for low exothermic loss tangent, storage elastic modulus, and wear resistance>
(1) Low exothermic property and storage elastic modulus Low exothermic property was evaluated by the reciprocal of loss tangent. The storage elastic modulus (G ′) and loss tangent (tan δ) were measured at a temperature of 50 ° C., a frequency of 15 Hz, and a strain of 5% using a viscoelasticity measuring device manufactured by Rheometrics. The low exothermic property was expressed as an index with the reciprocal of the loss tangent (tan δ) as 100, and the storage elastic modulus index was expressed as an index with the storage elastic modulus (G ′) of Comparative Example 1 as 100. The low exothermic property indicates that the lower the exothermic index value, the better the low exothermic property. Moreover, it has shown that the storage elastic modulus is so high that the index value of storage elastic modulus (G ') is large.

(2) Abrasion resistance For the measurement of the abrasion resistance, a Lambourn abrasion tester was used according to JIS K 6264-2: 2005. The amount of wear when the slip rate at room temperature (23 ° C.) was 25% was measured and displayed as an index with the reciprocal of the amount of wear of Comparative Example 1 serving as a reference as 100. It shows that it is excellent in abrasion resistance, so that the value of this index | exponent is large.

表１に示した各成分は、下記のものを用いた。
・高シス１，４−ポリブタジエンゴム（ＪＳＲ株式会社製 ＢＲ０１）
・カーボンブラック：東海カーボン(株)製, 商標：シーストＫＨ（Ｎ３３９）
・シリカ：日本シリカ工業(株)製, 商標：ニプシルＡＱ
・シランカップリング剤：デグサ社製, 商標Ｓｉ６９
・老化防止剤：Ｎ−（１，３−ジメチルブチル）−Ｎ’−ｐ−フェニレンジアミン、大内新興化学（株）製、ノックラック６Ｃ
・加硫促進剤ＣＺ−Ｇ：Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、大内新興化学（株）製、ノクセラーＣＺ−Ｇ
・加硫促進剤ＤＭ−Ｐ：ジベンゾチアゾリルジスルフィド、大内新興化学（株）製、ノクセラーＤＭ−Ｐ

The following were used for each component shown in Table 1.
・ High cis 1,4-polybutadiene rubber (BR01 manufactured by JSR Corporation)
・ Carbon black: manufactured by Tokai Carbon Co., Ltd., trademark: Seast KH (N339)
・ Silica: Nippon Silica Kogyo Co., Ltd., Trademark: Nipsil AQ
Silane coupling agent: Degussa, trademark Si69
Anti-aging agent: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., knock rack 6C
・ Vulcanization accelerator CZ-G: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G
・ Vulcanization accelerator DM-P: Dibenzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM-P

  From the results shown in Table 1, the rubber compositions of Examples 1 to 4 in which the modified conjugated diene polymers 1 to 4 and a copolymer of a conjugated diene compound and a nonconjugated olefin were blended were conjugated dienes. Compared to the rubber composition of Comparative Example 1 in which a conjugated diene polymer in which the active terminal of the polymer-based polymer is not modified and a cis-type butadiene rubber is blended, low exothermic property, storage elastic modulus, and abrasion resistance Were found to be good.

  The low heat build-up and wear resistance of the rubber composition of Comparative Example 2 in which the modified conjugated diene polymer 1 and cis-type butadiene rubber were blended were the same as those of the rubber composition of Comparative Example 1. It can be seen that the storage modulus decreases.

  Further, the storage elastic modulus of the rubber composition of Comparative Example 3 in which the conjugated diene polymer in which the active terminal of the conjugated diene polymer is not modified and the copolymer of the conjugated diene compound and the non-conjugated olefin is blended is Although it was improved as compared with the elastic modulus of the rubber composition of Comparative Example 1, it was found that the low heat buildup and wear resistance were slightly increased, and sufficient effects could not be obtained.

  Since the rubber composition of the present invention can improve both low heat build-up, wear resistance and storage elastic modulus, it can be used for pneumatic tires, anti-vibration rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, It is suitably used for hoses and foams.

  DESCRIPTION OF SYMBOLS 1 ... Rubber laminated body, 11 ... 1st layer, 12 ... 2nd layer, 13 ... 3rd layer, 100 ... Tire, 111, 112 ... Bead core, 113, 114 ... Stiffener, 115a-115d ... Belt layer, 118 ... Tread Part, 121 ... carcass ply, 130 ... inner liner

Claims (14)

100 parts by mass of a rubber component containing 3 to 97% by mass of a modified conjugated diene polymer and 3 to 97% by mass of a copolymer of a conjugated diene compound and a non-conjugated olefin having a conjugated diene ratio of 30 to 80% by mol in contrast, a rubber composition containing 5 to 200 parts by weight of the charge Hamazai, the modified conjugated diene polymer rubber having a functional group having affinity with the filler in the molecule chain object.   The rubber composition according to claim 1, wherein the copolymer is at least one selected from a block copolymer and a tapered copolymer.   The rubber composition according to claim 1 or 2, wherein the copolymer has a cis 1,4 bond amount of a conjugated diene compound portion of 50% or more.   The rubber composition according to any one of claims 1 to 3, wherein the copolymer has a weight average molecular weight in terms of polystyrene of 10,000 to 10,000,000.   The rubber composition according to any one of claims 1 to 4, wherein a molecular weight distribution (Mw / Mn) of the copolymer is 15 or less.   The rubber composition according to any one of claims 1 to 5, wherein the non-conjugated olefin is an acyclic olefin.   The rubber composition according to claim 1, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The rubber composition according to claim 6 or 7, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The rubber composition according to claim 8, wherein the non-conjugated olefin is ethylene.   The rubber composition according to claim 1, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The functional group having an affinity for the filler is at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group. The rubber composition as described in 2.   The rubber composition according to any one of claims 1 to 10, wherein the modified conjugated diene polymer has a functional group having an affinity for the filler at a molecular chain terminal. The functional group having an affinity for the filler is at least selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, a functional group containing silicon and nitrogen, and a secondary amino group derived from a lithium amide compound. the rubber composition according to any one of which is a kind of functional group claim 1-12. A tire using the rubber composition according to any one of claims 1 to 13 .

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