JP2013170233A - Rubber composition for tire and pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for a tire capable of maintaining an appearance of a tire in a good condition without degrading ozone resistance, and to provide a pneumatic tire.SOLUTION: A rubber composition for a tire comprises a rubber component, which includes at least one of a diene synthetic rubber and natural rubber, and a conjugate diene compound-nonconjugate olefin copolymer, and which is blended with, as a surfactant, at least one compound selected from the group consisting of a polyethyleneglycol monocarboxylic acid ester, polyethyleneglycol monoalkylether, polyoxyethylene sorbitan fatty acid ester, and (five-member ring or six-member ring type) polyoxyalkylene alkenylether ammonium sulfate (expressed by general formula (e)).

Description

  The present invention relates to a tire rubber composition and a pneumatic tire.

  In general, a rubber article made from natural rubber or a diene synthetic rubber is deteriorated in the presence of ozone, and a crack occurs on the surface. This crack progresses due to static and dynamic stress applied to the rubber article, and as a result, the rubber article is broken. In order to suppress the occurrence and progression of cracks due to ozone, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine or the like is used as an anti-aging agent in rubber articles, particularly tire treads. A rubber composition containing an amine anti-aging agent is applied.

  The rubber composition contains a wax for forming a protective film on the surface of the rubber article for the purpose of static protection from ozone.

  However, the amine anti-aging agent and the wax are effective in suppressing the generation of cracks in the presence of ozone and the progress thereof, but easily move through a polymer substrate such as a rubber component, and in a short period, a rubber article, In particular, it shifts to the surface of the tire and deteriorates the appearance by changing the color of the rubber article during storage and use. Here, when the wax moves to the surface, the surface turns white, and when the amine-based anti-aging agent moves to the surface, the surface turns brown.

  In recent years, there is a case where it is required to give gloss to a rubber article, particularly a tire, to make the appearance beautiful, and a technique for suppressing discoloration is required.

  Therefore, a technology for preventing discoloration due to an amine anti-aging agent and wax by blending a polyoxyethylene ether type nonionic surfactant or a sorbitan type surfactant with a rubber composition for a tire sidewall is known. (For example, refer to Patent Documents 1 and 2).

  In recent years, technological development has been carried out with the aim of reducing rubber gauges in order to save resources and improve fuel efficiency by reducing tire weight. However, as the rubber gauge becomes smaller, the absolute amount of anti-aging agent in the rubber is reduced. It becomes smaller, and ozone deterioration tends to occur. It is also important to prevent such ozone degradation.

  Conventionally, a conjugated diene compound-nonconjugated olefin copolymer (a copolymer of a conjugated diene compound and a nonconjugated olefin) and a tire rubber composition containing the same have been studied.

  For example, Patent Document 3 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.

  Patent Document 4 discloses an olefin polymerization catalyst comprising a transition metal compound such as a titanium compound and a cocatalyst, and discloses a copolymer of an α-olefin and a conjugated diene compound.

  Further, Patent Document 5 discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component.

  Patent Document 6 discloses a butadiene polymer having a cis content of 92% and an ethylene content of 3% or 9%.

  However, a tire rubber composition capable of sufficiently maintaining the appearance of a tire without deteriorating ozone resistance has not been obtained yet, and development thereof has been strongly desired.

JP 2001-200105 A JP 2004-307812 A JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141 JP 2000-86857 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a rubber composition for a tire and a pneumatic tire that can maintain a good appearance of the tire without deteriorating ozone resistance.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have used a conjugated diene compound-non-conjugated olefin copolymer and a predetermined surfactant in combination with a tire rubber composition, thereby preventing ozone resistance. As a result, it was found that the appearance of the tire can be kept good without deteriorating the properties, and the present invention has been completed.

［一般式（ａ）において、Ｒは、炭素数１〜１８のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｎは、１〜３０の整数を表す。］

［一般式（ｂ）において、Ｒは、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｎは、１〜３０の整数を表す。］

［一般式（ｃ）において、Ｒ₁は、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｌ、ｍ及びｎは、それぞれ独立して、１〜５０の整数を表し、ｌ、ｍ及びｎの総和が３〜５０を表す。］

［一般式（ｄ）において、Ｒ₁は、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｌ、ｍ及びｎは、それぞれ独立して、１〜５０の整数を示し、ｌ、ｍ及びｎの総和が３〜５０を表す。］

［一般式（ｅ）において、Ｒ_ｌは、炭素数１〜４のアルキレン基、又は、置換基として炭素数１から１０のアルキル基を有していてもよいアリーレン基を表し、Ｒ_２は、水素又はメチル基を表し、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、水素、炭素数１〜１８のアルキル基、又は、炭素数２〜４のアルカノール基を表し、Ａ_ｌは、炭素数４のアルキレン基を表し、Ａ_２は、炭素数２〜３のアルキレン基を表す。ｎは、０〜２０の整数を表し、ｍは、１〜５０の整数を表す。］
前記タイヤ用ゴム組成物が界面活性剤を含むことにより、アミン系老化防止剤やワックスが表面に移行して変色するのを防止することができる。また、前記タイヤ用ゴム組成物が界面活性剤を含むことで、耐オゾン性は低下しない。 The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is, the tire rubber composition of the present invention is a tire rubber composition comprising a rubber component containing at least one of a diene synthetic rubber and a natural rubber and a conjugated diene compound-nonconjugated olefin copolymer, The activator is characterized by blending at least one selected from the group consisting of compounds represented by the following general formulas (a) to (e).

[In General Formula (a), R represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , Represents an integer of 1 to 30. ]

[In the general formula (b), R represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , Represents an integer of 1 to 30. ]

[In General Formula (c), R ₁ represents an alkyl or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

[In General Formula (d), R ₁ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

[In the general formula (e), R _l represents an alkylene group having 1 to 4 carbon atoms, or an arylene group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, R ₂ is represents hydrogen or a methyl _group, R 3, _{R 4} and _{R 5} each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkanol group having 2 to 4 carbon atoms, _{a l} is Represents an alkylene group having 4 carbon atoms, and A ₂ represents an alkylene group having 2 to 3 carbon atoms. n represents an integer of 0 to 20, and m represents an integer of 1 to 50. ]
When the tire rubber composition contains a surfactant, it is possible to prevent the amine-based anti-aging agent and wax from being transferred to the surface and discolored. Moreover, ozone resistance does not fall because the said rubber composition for tires contains surfactant.

  The tire rubber composition of the present invention preferably contains 0.1 to 10 parts by mass of the surfactant with respect to 100 parts by mass of the rubber component.

  In the tire rubber composition of the present invention, it is preferable that the tire rubber composition further contains an amine-based antioxidant.

  In the tire rubber composition of the present invention, the tire rubber composition preferably further contains a wax, and the wax is preferably microcrystalline or paraffin wax.

  In the tire rubber composition of the present invention, the cis 1,4-bond content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is preferably more than 92%.

  In the tire rubber composition of the present invention, the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer is preferably 50 mol% or less.

  The rubber composition for tires of the present invention has a content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer. 5% or less is preferable.

  In the tire rubber composition of the present invention, the molecular weight distribution (Mw / Mn) of the conjugated diene compound-nonconjugated olefin copolymer is preferably 10 or less.

  In the tire rubber composition of the present invention, the non-conjugated olefin is preferably an acyclic olefin.

  In the tire rubber composition of the present invention, the non-conjugated olefin preferably has 2 to 10 carbon atoms.

  In the tire rubber composition of the present invention, the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene and 1-butene.

  In the tire rubber composition of the present invention, the non-conjugated olefin is preferably ethylene.

  In the tire rubber composition of the present invention, the conjugated diene compound preferably has 4 to 8 carbon atoms.

  In the tire rubber composition of the present invention, the conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

  In the tire rubber composition of the present invention, the conjugated diene compound-nonconjugated olefin copolymer is preferably a butadiene-ethylene copolymer.

  The pneumatic tire of the present invention is characterized by using the tire rubber composition.

  According to the present invention, it is possible to solve the conventional problems, achieve the object, and maintain a good tire appearance without deteriorating ozone resistance, and a tire rubber composition and pneumatic Tires can be provided.

Hereinafter, embodiments of the present invention will be specifically described.
(Rubber composition for tire)
The tire rubber composition of the present invention is not particularly limited as long as it contains a rubber component and a surfactant (appearance improver), and can be appropriately selected according to the purpose. It preferably contains an agent, wax, carbon black, white filler (inorganic filler), cross-linking agent, and other components.

<Rubber component>
The rubber component is not particularly limited as long as it contains at least one of a diene synthetic rubber and natural rubber and a conjugated diene compound-nonconjugated olefin copolymer, and can be appropriately selected according to the purpose.

-Diene-based synthetic rubber-
There is no restriction | limiting in particular as said diene type synthetic rubber, Although it can select suitably according to the objective, For example, various butadiene rubber (BR), various styrene-butadiene copolymer rubber (SBR), isoprene rubber, butyl rubber Halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, Etc. These may be used individually by 1 type and may use 2 or more types together.

—Natural Rubber— The natural rubber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include RSS # 3.

-Conjugated diene compound-Non-conjugated olefin copolymer-
There is no restriction | limiting in particular as content in the rubber component of the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 3 mass% or more is preferable.
When the content of the conjugated diene compound-nonconjugated olefin copolymer in the rubber component is less than 3% by mass, the effect of improving crack growth resistance, heat resistance, and ozone resistance is small or improved. It may not be effective.

The cis 1,4-bond content of the conjugated diene compound-derived moiety (conjugated diene moiety) in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the purpose. More than 92% is preferable, and 95% or more is more preferable.
When the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is more than 92%, it is possible to improve crack growth resistance, weather resistance, and heat resistance.
Moreover, it is more advantageous that the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is 95% or more in terms of crack growth resistance, weather resistance, and heat resistance.
The amount of cis-1,4 bonds is the amount in the portion derived from the conjugated diene compound, and is not a ratio relative to the entire copolymer.

  The non-conjugated olefin used as the monomer is a non-conjugated olefin other than the conjugated diene compound, and has excellent heat resistance and reduces the proportion of double bonds in the main chain of the copolymer and controls crystallinity. This makes it possible to increase the degree of design freedom as an elastomer.

As content of the nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, 50 mol% or less is preferable and it is preferable that it is less than 10 mol%.
When the content of the non-conjugated olefin-derived portion exceeds 50 mol%, kneadability and workability with the filler may become a problem.

  The non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin is preferably an α-olefin having 2 to 10 carbon atoms. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with the conjugated diene can be performed efficiently. 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 8 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 conjugated diene compound-nonconjugated olefin copolymer can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  In addition, when a block portion composed of a monomer unit of a non-conjugated olefin is provided, it exhibits static crystallinity and can be excellent in mechanical properties such as breaking strength.

  The conjugated diene compound-nonconjugated olefin copolymer has no problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. Therefore, the polystyrene-converted weight average molecular weight (Mw) of this copolymer is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and further 50,000 to 600,000. preferable. If Mw exceeds 10,000,000, the moldability may be deteriorated.

The conjugated diene compound-nonconjugated olefin copolymer 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. . Furthermore, 2% or less is preferable.
The conjugated diene compound-nonconjugated olefin copolymer has an anti-wrinkle resistance when the conjugated diene compound-derived part has a 1,2-adduct part (including 3,4-adduct part) content of 5% or less of the conjugated diene compound. And ozone resistance can be further improved.
The content of the 1,2 adduct portion (including the 3,4 adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole 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) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not 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).

Next, a production method capable of producing the conjugated diene compound-nonconjugated olefin copolymer will be described in detail. However, the manufacturing method described in detail below is merely an example.
The conjugated diene compound-nonconjugated olefin copolymer can polymerize a conjugated diene compound and a nonconjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition shown below. 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 inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  According to the above production method, except that the polymerization catalyst or the polymerization catalyst composition is used, the monomer conjugated diene compound and the non-conjugated compound are produced in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst. 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、該重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。ここで、メタロセン錯体は、一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／Ｌの範囲であることが好ましい。 <First polymerization catalyst composition>
The polymerization catalyst composition includes 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 unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called 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 general formula (I) and formula (II), Cp ^R in the formula is an unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may 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 ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） 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.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^R ′ having the above indenyl ring as the basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are 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 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.

  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) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{a to} R ^f in the general formula (I)) 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 ^{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 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 thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group 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 any of 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.

  Further, 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.

（式中、Ｘ’’はハライドを示す。） 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.

(In the formula, X ″ represents a halide.)

（式中、Ｘ’’はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a 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 ′ independently represents 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.

[A] Examples of the cation represented by ⁺ 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, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. Further, the ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to 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 a metallocene complex represented by the general formula (I) or the formula (II) and an 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 above 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 each used as an appropriate promoter. By combining, the molecular weight of the cis-1,4 bond amount and the resulting conjugated diene compound-nonconjugated olefin copolymer can be increased.

<Second polymerization catalyst composition>
In addition, as the 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 containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds (hereinafter also referred to as a second polymerization catalyst composition) can be preferably exemplified.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: 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]. It is characterized by including.

The second polymerization catalyst composition used in the method for producing the conjugated diene compound-nonconjugated olefin copolymer needs to contain the component (A) and the component (B), where the polymerization catalyst composition is In the case where at least one of the ionic compound (B-1) and the halogen compound (B-3) is contained,
(C) Component: 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]. 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 reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth element 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)
[Wherein 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. Represents 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, thio aliphatic thiolate groups such as sec-butoxy group and thio-tert-butoxy group; Noxy 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-tert-butyl Arylamide groups such as ru-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups 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, iodine And halogen atoms such as atoms. 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. It 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 of the 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, as well as III, IV, 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 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 and third polymerization catalyst composition>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 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、Ｍ^１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、Ｍ^１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。 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 independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently represent a group having 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 represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by

  The third polymerization catalyst composition includes the metallocene composite catalyst and a boron anion.

<Metalocene composite catalyst>
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 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.] By using the metallocene polymerization catalyst, a conjugated diene compound-nonconjugated olefin copolymer 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. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. 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. Preferable 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 may 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. Incidentally, the two Cp ^R in the formula (XV) may each be the same 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、Ｍ^２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よいので、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よい。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 has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3, and a metallocene complex 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. In addition, 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 synthesis of the catalyst becomes easy. 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.

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

On the other hand, the organoaluminum compound used for the production of 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. hydrogen group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that, R ^M may be the same or different and the R ^K or R ^L. 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. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

<Third polymerization catalyst composition>
The polymerization catalyst composition contains the 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, as in the metallocene composite catalyst, since it further contains a boron anion, the content of each monomer component in the conjugated diene compound-nonconjugated olefin copolymer Can be controlled arbitrarily.

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. In addition, it is preferable to add 0.1-10 times mole with respect to the said metallocene type composite catalyst, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 time mole.

  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. These aluminoxanes may be used alone or in combination of two or more.

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer, as described above, a method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. Similarly, polymerization can be carried out. Here, the method for producing a conjugated diene compound-nonconjugated olefin copolymer includes, for example, (1) a polymerization catalyst in a polymerization reaction system containing a conjugated diene compound as a monomer and a nonconjugated olefin other than the conjugated diene compound. The components of the composition 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 mole 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 a conjugated diene compound-nonconjugated olefin copolymer, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer, the polymerization reaction of the conjugated diene compound and the nonconjugated 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 method for producing the conjugated diene compound-nonconjugated olefin copolymer, when the conjugated diene compound is polymerized with a nonconjugated olefin other than the conjugated diene compound, the pressure of the nonconjugated olefin is 0.1 MPa to 10 MPa. It is preferable. 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 method for producing the conjugated diene compound-nonconjugated olefin copolymer, when the conjugated diene compound is polymerized with a nonconjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l). ) And the concentration (mol / l) of the non-conjugated olefin are represented by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. 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.

-Other rubber components-
The other rubber component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, bromide of copolymer of isobutylene and p-methylstyrene, ethylene-propylene copolymer rubber, chlorosulfonated Examples thereof include polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, and urethane rubber.

<Surfactant (appearance improver)>
Moreover, in order to suppress discoloration and improve the appearance, at least one selected from the compounds represented by the following general formulas (a) to (e) as a surfactant (appearance improver) is used for tires. You may make it mix | blend with a rubber composition.

［一般式（ａ）において、Ｒは、炭素数１〜１８のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｎは、１〜３０の整数を表す。］

[In General Formula (a), R represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , Represents an integer of 1 to 30. ]

［一般式（ｂ）において、Ｒは、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｎは、１〜３０の整数を表す。］

[In the general formula (b), R represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , Represents an integer of 1 to 30. ]

［一般式（ｃ）において、Ｒ₁は、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｌ、ｍ及びｎは、それぞれ独立して、１〜５０の整数を表し、ｌ、ｍ及びｎの総和が３〜５０を表す。］

[In General Formula (c), R ₁ represents an alkyl or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

［一般式（ｄ）において、Ｒ₁は、炭素数１〜２０のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく；ｌ、ｍ及びｎは、それぞれ独立して、１〜５０の整数を示し、ｌ、ｍ及びｎの総和が３〜５０を表す。］

[In General Formula (d), R ₁ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

［一般式（ｅ）において、Ｒ_ｌは、炭素数１〜４のアルキレン基、又は、置換基として炭素数１から１０のアルキル基を有していてもよいアリーレン基を表し、Ｒ_２は、水素又はメチル基を表し、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、水素、炭素数１〜１８のアルキル基、又は、炭素数２〜４のアルカノール基を表し、Ａ_ｌは、炭素数４のアルキレン基を表し、Ａ_２は、炭素数２〜３のアルキレン基を表す。ｎは、０〜２０の整数を表し、ｍは、１〜５０の整数を表す。］

[In the general formula (e), R _l represents an alkylene group having 1 to 4 carbon atoms, or an arylene group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, R ₂ is represents hydrogen or a methyl _group, R 3, _{R 4} and _{R 5} each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkanol group having 2 to 4 carbon atoms, _{a l} is Represents an alkylene group having 4 carbon atoms, and A ₂ represents an alkylene group having 2 to 3 carbon atoms. n represents an integer of 0 to 20, and m represents an integer of 1 to 50. ]

-Compound represented by general formula (a)-
As long as it is 1-18 as carbon number of R in General formula (a), there is no restriction | limiting in particular, Although it can select suitably according to the objective, 2-18 are the points of the solubility to rubber | gum. Preferably, 6-18 is more preferable, and 6-15 is further more preferable.
The range of n in the general formula (a) is not particularly limited as long as it is 1 to 30, and can be appropriately selected according to the purpose, but is preferably 10 to 30, more preferably 10 to 25, and 16 ~ 25 is particularly preferred.
Suitable commercially available products of the compound represented by formula (a), is not particularly limited and may be appropriately selected depending on the purpose, for example, (i) a non-ionic surfactant (R = C ₁₁ H23 _, n = 12) (HLB = 13.7): Trademark “Emanon 1112” (manufactured by Kao Corporation), (ii) nonionic surfactant (R = C ₁₇ H ₃₅ , n = 10) (HLB) = 11.6): Trademark “Emanon 4110” (manufactured by Kao Corporation), (iii) polyoxyethylene monostearate (R = C ₁₇ H ₃₅ , n = 13) (HLB = 13.4), (iv) And polyoxyethylene monostearate (R = C ₁₁ H ₂₃ , n = 22) (HLB = 16.7).

-Compound represented by general formula (b)-
The carbon number of R in the general formula (b) is not particularly limited as long as it is 1 to 20, and can be appropriately selected according to the purpose. However, in terms of the solubility in rubber and the bloom speed, 6 ~ 20 is preferred.
The range of n in the general formula (b) is not particularly limited as long as it is 1 to 30, and can be appropriately selected according to the purpose, but is preferably 2 to 30, more preferably 2 to 25, and 2 ~ 18 is particularly preferred.
Suitable commercially available products of the compound represented by the general formula (b), is not particularly limited and may be appropriately selected depending on the purpose, for example, (i) a non-ionic surfactant (R = C ₁₁ H ₂₃ , n = 18): Trademark “Emulgen 1118” (manufactured by Kao Corporation), (ii) Nonionic surfactant (R = C ₁₁ H ₂₃ , n = 18): Trademark “Emulgen 1108” (Kao Corporation) (Iii) Nonionic surfactant (R = C ₁₂ H ₂₅ , n = 23): Trademark “Emulgen 123” (manufactured by Kao Corporation), (iv) R is alkyl having 13 to 15 carbon atoms And a compound in which n = 4 (synchronic A4, manufactured by UNIQEMA), and the like.

-Compound represented by formula (c) or (d)-
The carbon number of R _{1 in} the general formula (c) or (d) is not particularly limited as long as it is 1 to 20, and can be appropriately selected according to the purpose, but from the viewpoint of solubility in rubber. 8-18 are preferable, and 12-18 are more preferable.
The ranges of l, m, and n in the general formula (c) or (d) are not particularly limited as long as they are independently 1 to 50, and can be appropriately selected according to the purpose. -30 are preferable and 1-20 are more preferable.
The range of the sum of l, m, and n in the general formula (c) or (d) is not particularly limited as long as it is 3 to 50, and can be appropriately selected according to the purpose. 6-20 are more preferable.
There is no restriction | limiting in particular as a suitable commercial item of the compound represented by general formula (c) or (d), According to the objective, it can select suitably, For example, (i) nonionic surfactant ( R = C ₁₁ H ₂₃ , l + m + n = 20) (HLB = 16.7): Trademark “Leodol TW-L120” (manufactured by Kao Corporation), (ii) nonionic surfactant (R = C ₁₁ H ₂₃ , l + m + n = 6) (HLB = 13.3): Trademark “Leodol TW-L106” (manufactured by Kao Corporation), (iii) nonionic surfactant (R = C ₁₈ H ₃₅ , l + m + n = 6) (HLB = 9.6): Trademark “Leodol TW-S106” (manufactured by Kao Corporation), and the like.

-Compound represented by general formula (e)-
The range of n in the general formula (e) is not particularly limited as long as it is 0 to 20, and can be appropriately selected according to the purpose, but 0 to 10 is preferable from the viewpoint of solubility in rubber. .
The range of m in the general formula (e) is not particularly limited as long as it is 1 to 50, and can be appropriately selected according to the purpose, but 1 to 30 is preferable from the viewpoint of solubility in rubber. 1-20 are more preferable.
There is no restriction | limiting in particular as ion represented by NR < ₃ > R < ₄ > R < ₅ > in General formula (e), Although it can select suitably according to the objective, Ammonium ion, a triethylamine ion, a tributylamine ion, a triethanolamine Ion and dimethylstearylamine ion are preferred.
Suitable commercially available products of the compound represented by the formula (e), is not particularly limited and may be appropriately selected depending on the purpose, for example, (i) a ionic surfactant (R ₁ is CH ₂ R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 6; m = 15) (manufactured by Kao Corporation), (ii) ionic surfactant (R ₁ is CH ₂ ; R ₂ ; Is CH ₃ ; R ₃ , R ₄ and R ₅ are ethanol; n = 6; m = 15) (manufactured by Kao Corporation), (iii) ionic surfactant (R ₁ is CH ₂ ; R ₂ is CH ₃ R ₃ and R ₄ are stearyl groups; R ₅ is H; n = 6; m = 15) (manufactured by Kao Corporation), (iv) ionic surfactant (R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 3; m = 15) (manufactured by Kao Corporation), (v) ionic surfactant (R ₁ is C H ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 3; m = 10) (manufactured by Kao Corporation), (vi) ionic surfactant (R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 7; m = 20) (manufactured by Kao Corporation), (vii) an ionic surfactant (R ₁ is CHC ₉ H ₁₉ and A mixture of CHC ₁₁ H ₂₃ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 0; m = 10) (manufactured by Kao Corporation), and the like.

There is no restriction | limiting in particular as content with respect to 100 mass parts of rubber components of the said surfactant, Although it can select suitably according to the objective, 0.1 mass part-10 mass parts are preferable.
When the content of the surfactant with respect to 100 parts by mass of the rubber component is less than 0.1 parts by mass, the effect of preventing discoloration due to an amine anti-aging agent or wax and the effect of giving gloss to the surface may be small. When it exceeds the mass part, gloss due to the bloom of the surfactant becomes excessive and the appearance may be deteriorated, or a problem may occur in the surface tackiness and workability may be deteriorated.

<Amine-based anti-aging agent>
In order to suppress the generation and progression of cracks due to ozone, the rubber composition for tires is preferably blended with an amine-based anti-aging agent.
There is no restriction | limiting in particular as said amine type anti-aging agent, According to the objective, it can select suitably, For example, N-phenyl-p-phenylenediamine etc. are mentioned.

<Wax>
The tire rubber composition preferably contains a wax in order to suppress the occurrence and progression of cracks due to ozone.
The wax is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include microcrystalline and paraffin wax.

<Carbon black>
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Nitrogen adsorption specific surface area of the carbon black: The (N ₂ SA, JIS K 6217-2 compliant 2001) is not particularly limited and may be appropriately selected depending on the intended purpose, 50 m ² / g than that preferably, 70m ² / g~130m ² / g is more preferable.
When the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 50 m ² / g or less, the reinforcing effect is low and sufficient durability may not be obtained.
Incidentally, the nitrogen adsorption specific surface area (N ₂ SA), for example, JIS K 6217-2: can conform to 2001, measured.
There is no restriction | limiting in particular as content of carbon black with respect to 100 mass parts of said rubber components, Although it can select suitably according to the objective, 10 mass parts-70 mass parts are preferable, and 20 mass parts-60 mass parts are. More preferred.
If the carbon black content is less than 10 parts by mass, the reinforcing property may be insufficient and the fracture resistance may deteriorate, and if it exceeds 70 parts by mass, the workability and low loss property may deteriorate. is there.
On the other hand, when the content of the carbon black is within the more preferable range, it is advantageous in terms of the balance of each performance.

<White filler (inorganic filler)>
The white filler (inorganic filler) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, and glass. Examples thereof include beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together.
In addition, when using a white filler (inorganic filler), you may use a silane coupling agent suitably.

There is no restriction | limiting in particular as content of the said white filler (inorganic 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.
When the content of the white filler (inorganic filler) is less than 5 parts by mass, the effect of adding the white filler (inorganic filler) may not be seen so much. When the content exceeds 200 parts by mass, the rubber There is a tendency that a white filler (inorganic filler) is not mixed into the component, and the performance as a rubber composition may be lowered.

-Silica-
The silica is not particularly limited and can be appropriately selected depending on the purpose, and any commercially available product can be used. Among them, it is preferable to use wet silica, dry silica, colloidal silica, particularly wet. It is particularly preferable to use silica. When silica is used as the reinforcing filler, the silane coupling agent can be contained in an amount of about 1% by mass to 20% by mass with respect to the silica from the viewpoint of reinforcing properties. It is preferable to contain about 6% by mass to 12% by mass.

<Crosslinking agent>
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents, sulfur and the like can be mentioned, among which sulfur-based crosslinking agents are more preferable as the rubber composition for tires.

There is no restriction | limiting in particular as content of the said 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.
When the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking hardly proceeds, and when the content exceeds 20 parts by mass, the cross-linking tends to progress during kneading with a part of the cross-linking agent. The physical properties of the sulfide may be impaired.

<Other ingredients>
In addition, it is also possible to use a vulcanization accelerator in combination, and examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
If necessary, compounding agents usually used in the rubber industry such as vulcanizing agents, scorch preventing agents, softeners, zinc oxide, stearic acid, and silane coupling agents are appropriately selected within a range that does not impair the purpose of the present invention. Can be selected and blended. As these compounding agents, commercially available products can be suitably used. In addition, the said rubber composition can be manufactured by knead | mixing a rubber component, the said thermosoftening resin, and the various compounding agents selected suitably as needed, heat-inserting, extrusion, etc.

(Pneumatic tire)
The pneumatic tire of the present invention is not particularly limited as long as it uses the tire rubber composition of the present invention, and can be appropriately selected according to the purpose, for example, applied to a tread or a sidewall. Is preferred.
As a method for manufacturing the tire, a conventional method can be used. For example, members used in normal tire production such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber and / or cord are sequentially laminated on a tire molding drum, and the drum is removed to obtain a green tire. Next, a desired pneumatic tire can be manufactured by heating and vulcanizing the green tire according to a conventional method.
The pneumatic tire has a good appearance over a long period of time because the amine-based anti-aging agent and the wax are prevented from being transferred to the tire surface and discolored.

  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.

(Preparation Example 1)
After 150 ml of toluene was added to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.4 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilyl) amide [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 14.5 μmol in a glass container. Then, 14.1 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) and 0.87 mmol of diisobutylaluminum hydride 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. Then, it was vacuum dried at 70 ° C. to obtain a copolymer A. The yield of the obtained copolymer A was 20.00 g.

  For the copolymer A obtained as described above and the obtained high cis-butadiene rubber (HCBR) (trade name: BR01, manufactured by JSR), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn), The 1,2-vinyl bond content, cis-1,4 bond content, and ethylene-derived partial content were measured and evaluated by the following methods.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Using gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)], measuring temperature 140 The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined on the basis of monodisperse polystyrene at ° C. The results are shown in Table 1.
(2) Microstructure (1,2-vinyl bond amount, cis-1,4 bond amount)
The microstructure (1,2-vinyl bond content) of the butadiene moiety in the copolymer was determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm), with a 1,2-vinyl bond component (5.0 ppm). -5.1 ppm) and the total butadiene bond component (5 ppm-5.6 ppm), and the microstructure of the butadiene moiety in the copolymer (cis-1,4 bond) was determined by ¹³ C-NMR spectrum ( 100 ° C., d-tetrachloroethane standard: 73.8 ppm) and cis-1,4 binding component (26.5 ppm-27.5 ppm) and total butadiene binding component (26.5 ppm-27.5 ppm + 31.5 ppm-32.5 ppm) ). The calculated values of 1,2-vinyl bond amount (%) and cis-1,4 bond amount (%) are shown in Table 1.
(3) Content of ethylene-derived part The content (mol%) of the ethylene-derived part in the copolymer was determined by ¹³ C-NMR spectrum (100 ° C, d-tetrachloroethane standard: 73.8 ppm) as a whole ethylene-bonded component. (28.5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). Table 1 shows the content (mol%) of the ethylene-derived portion.

  Further, as shown in Preparation Examples 2 and 3 below, nonionic surfactants were prepared.

(Preparation Example 2)
In a 500 mL four-necked flask, weigh 240.0 g of polyethylene glycol 600 (reagent; molecular weight 600), 114.0 g of stearic acid (manufactured by Kao: Lunac S-90V), and 0.18 g of dibutyltin oxide (reagent) as a catalyst. The temperature was raised to 230 ° C. under nitrogen blowing, and the esterification reaction was continued until the acid value became 2.0 mgKOH / g or less. Thereafter, the liquid temperature is cooled to 60 ° C. to 70 ° C., 0.19 g of 85% phosphoric acid (reagent) is added, and stirring is continued for 30 minutes. Further, 0.7 g of KYOWARD 600S (adsorbent; manufactured by Kyowa Chemical Industry Co., Ltd.) is added, and stirring is continued at this temperature for 30 minutes. Thereafter, vacuum filtration was performed using a filter aid to obtain PEG600 monostearate (POE13 monostearate).

(Preparation Example 3)
In a 500 mL four-necked flask, weigh 300.0 g of polyethylene glycol 1000 (reagent; molecular weight 1000) and 60.0 g of lauric acid (manufactured by Kao: Lunac L-98), and weigh 0.18 g of dibutyltin oxide (reagent). Under the same conditions as in Preparation Example 2, PEG 1000 monolaurate (POE22 monolaurate) was obtained.

(Examples 1-19, Comparative Examples 1-2)
For Examples 1 to 19 and Comparative Examples 1 and 2, the rubber compound was prepared with the formulation and formulation shown in Formulation 1 in Table 2 and the type and addition amount of the surfactants shown in Table 3, and 160 ° C. The test piece of vulcanized rubber was produced by vulcanizing for 20 minutes. The produced test piece was subjected to the following ozone resistance evaluation and discoloration degree evaluation. The obtained results are shown in Table 3.
In Comparative Example 1, BR (HCBR) was used, and in Examples 1 to 19 and Comparative Example 2, EBR (Copolymer A) was used.

(Examples 20 to 29, Comparative Examples 3 to 4)
For Examples 20 to 29 and Comparative Examples 3 to 4, a rubber compound was prepared with the compounding formulation shown in Formulation 2 in Table 2 and the type and addition amount of the surfactant shown in Table 4, and 160 ° C. The test piece of vulcanized rubber was produced by vulcanizing for 20 minutes. The produced test piece was subjected to the following ozone resistance evaluation and discoloration degree evaluation. Table 4 shows the obtained results.
In Comparative Example 3, BR (HCBR) was used, and in Examples 20 to 29 and Comparative Example 4, EBR (Copolymer A) was used.

(Examples 30 to 46, Comparative Examples 5 to 6)
For Examples 30 to 46 and Comparative Examples 5 to 6, a rubber compound was prepared with the compounding formulation shown in Formulation 3 in Table 2 and the type and addition amount of the surfactant shown in Table 5, and 160 ° C. The test piece of vulcanized rubber was produced by vulcanizing for 20 minutes. The produced test piece was subjected to the following ozone resistance evaluation and discoloration degree evaluation. The results obtained are shown in Table 5.
In Comparative Example 5, BR (HCBR) was used, and in Examples 30 to 46 and Comparative Example 6, EBR (Copolymer A) was used.

(Examples 47 to 51, Comparative Examples 7 to 8)
For Examples 47 to 51 and Comparative Examples 7 to 8, a rubber compound was prepared with the compounding formulation shown in Formulation 1 in Table 2 and the type and addition amount of the surfactant shown in Table 6, and 160 ° C. The tire was vulcanized for 20 minutes to obtain a vulcanized rubber, and a radial tire for a passenger car having a tire size of 205 / 65R15 in which the obtained vulcanized rubber was blended in a sidewall was prepared by a conventional method. The produced tire was subjected to the following ozone resistance evaluation and discoloration degree evaluation.
In Comparative Example 7, BR (HCBR) was used, and in Examples 47 to 51 and Comparative Example 8, EBR (Copolymer A) was used.

<Ozone resistance evaluation>
According to JIS K6301, ozone resistance evaluation was performed about the test piece produced in Examples 1-46 and Comparative Examples 1-6 on the conditions of temperature 40 degreeC, ozone density | concentration 50pphm, and elongation 20%. The deterioration state of the test piece was observed after 50 hours and evaluated based on the following criteria. Depending on the number of cracks generated, evaluation was made in three stages from A (small number of cracks) to C (number of cracks). Moreover, it evaluated in five steps of 1 (thing which cannot be seen with the naked eye, but can be confirmed with a 10 times magnifier) to 5 (thing which is likely to cause a crack or cut of 3 mm or more) depending on the size and depth of the crack.
Regarding the tests of tires manufactured in Examples 47 to 51 and Comparative Examples 7 to 8, new tire sidewalls were cut out and performed in the same manner as described above.

<Discoloration evaluation>
Evaluation was made using a colorimeter. The colorimeter evaluated the discoloration degree of the granular rubber test piece produced in Examples 1-46 and Comparative Examples 1-6 using "Nippon Denshoku Industries Co., Ltd. model name [NF333]". The colorimetric data was expressed as L *, a *, b *. L * value indicates lightness, and a * and b * indicate color. The a * value and the b * value are 0 and colorless, the positive the a * value, the more red and negative the green, and the b * value the more positive the yellow and negative the blue. For the degree of color change, the b * value immediately after vulcanization and the degree of color change immediately after vulcanization were evaluated based on the degree of color change immediately after vulcanization. The degree of discoloration after being allowed to stand was evaluated based on the b * value after leaving the vulcanized rubber piece for one month under the environmental conditions (direct sunlight only for a specific time) and the degree of color change visually. The degree of discoloration was evaluated on a five-point scale, with a value of 5 when discoloration was severely observed and 1 when discoloration was not observed.
Moreover, the same discoloration test as the above was performed also about the test of the tire produced in Examples 47-51 and Comparative Examples 7-8.

* 1 SBR # 1500 [manufactured by JSR Corporation]
* 2 BR (HCBR): JSR "JSR BR01"
* 2-2 Copolymer A prepared in Preparation Example 1
* 3 Seast 7HM [manufactured by Tokai Carbon Co., Ltd.]
* 4 N550 Carbon: "Asahi # 65" made by Asahi Carbon
* 5 "Nipseal VN3" manufactured by Tosoh Silica Corporation
* 6 Bis (3-ethoxysilylpropyl) tetrasulfide * 7 Microcrystalline wax: Ozoace 0280 [Nippon Seiwa Co., Ltd.]
* 8 Nocrack 6C [Ouchi Shinsei Chemical Co., Ltd.]
* 9 Non-flex RD-S [manufactured by Seiko Chemical]
* 10 Process oil: “Fukkor Aromax 3B” manufactured by Fujikosan
* 11 Noxeller D [Ouchi Shinsei Chemical Co., Ltd.]
* 12 Noxeller DM [Ouchi Shinsei Chemical Co., Ltd.]
* 13 Sunseller CM-G [manufactured by Sanshin Chemical Industry]

Compound A: Nonionic surfactant: Trademark “Emanon 1112” (manufactured by Kao Corporation) (the above general formula (a), R = C ₁₁ H _23, n = 12) (HLB = 13.7)
Compound B: Nonionic surfactant: Trademark “Emanon 4110” (manufactured by Kao Corporation) (the above general formula (a), R = C ₁₇ H ₃₅ , n = 10) (HLB = 11.6)
Compound C: Polyoxyethylene monostearate prepared in Preparation Example 2 (the above general formula (a), R = C ₁₇ H ₃₅ , n = 13) (HLB = 13.4)
Compound D: Polyoxyethylene monostearate prepared in Preparation Example 3 (formula (a), R = C ₁₁ H ₂₃ , n = 22) (HLB = 16.7)
Compound E: Nonionic surfactant: Trademark “Emulgen 1118” (manufactured by Kao Corporation) (general formula (b), R = C ₁₁ H ₂₃ , n = 18)
Compound F: Nonionic surfactant: Trademark “Emulgen 1108” (manufactured by Kao Corporation) (general formula (b), R = C ₁₁ H ₂₃ , n = 8)
Compound G: Nonionic surfactant: Trademark “Emulgen 123” (manufactured by Kao Corporation) (the above general formula (b), R = C ₁₂ H ₂₅ , n = 23)
Compound H: Nonionic surfactant: “Synchronic A4” (manufactured by UNIQEMA) (the general formula (b), a compound in which R is an alkyl chain having 13 to 15 carbon atoms and n = 4)
Compound I: Nonionic surfactant: Trademark “Leodol TW-L120” (manufactured by Kao Corporation) (general formula (c) or (d), R = C ₁₁ H ₂₃ , l + m + n = 20) (HLB = 16) .7)
Compound J: Nonionic surfactant: Trademark “Leodol TW-L106” (manufactured by Kao Corporation) (general formula (c) or (d), R = C ₁₁ H ₂₃ , l + m + n = 6) (HLB = 13) .3)
Compound K: Nonionic surfactant: Trademark “Leodol TW-S106” (manufactured by Kao Corporation) (general formula (c) or (d), R = C ₁₈ H ₃₅ , l + m + n = 6) (HLB = 9) .6)
Compound L: Sorbitan-based nonionic surfactant: Trademark “Leodol TW-S120V” (manufactured by Kao Corporation) (the above general formula (c) or (d), R = C ₁₈ H ₃₅ , l + m + n = 20) (HLB) = 14.9))
Compound M: Ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 6; m = 15)
Compound N: Ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are ethanol; n = 6; m = 15)
Compound O: Ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ and R ₄ are stearyl groups; R ₅ is H; n = 6; m = 15)
Compound P: Ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 3; m = 15)
Compound Q: Ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 3; m = 10)
Compound R: ionic surfactant: (manufactured by Kao Corporation) (general formula (e), R ₁ is CH ₂ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 7; m = 20)
Compound S: ionic surfactant: (manufactured by Kao Corporation) (the general formula (e), R ₁ is a mixture of CHC ₉ H ₁₉ and CHC ₁₁ H ₂₃ ; R ₂ is CH ₃ ; R ₃ , R ₄ and R ₅ are H; n = 0; m = 10)

From Tables 3 to 5, it can be seen that in any of Examples 1 to 46 with respect to Comparative Examples 1 to 6, the appearance is good without discoloration even after a certain time from immediately after vulcanization.
Moreover, it can be seen from Table 6 that, when Examples 47 to 51 and Comparative Examples 7 and 8 are compared, even if they are actually blended with tires, excellent effects are exhibited.
Furthermore, by adding a predetermined surfactant to the rubber composition, it exhibits a high effect on discoloration, and by adding a conjugated diene compound-nonconjugated olefin copolymer to the rubber composition, it exhibits high ozone properties. I understood.

  The rubber composition for tires of the present invention can be suitably used as a rubber composition for tire treads or a rubber composition for tire sidewalls.

Claims (17)

A tire rubber composition comprising a rubber component containing at least one of a diene synthetic rubber and a natural rubber and a conjugated diene compound-nonconjugated olefin copolymer,
A tire rubber composition comprising, as a surfactant, at least one selected from the group consisting of compounds represented by the following general formulas (a) to (e).

[In General Formula (a), R represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , Represents an integer of 1 to 30. ]

[In the general formula (b), R represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , Represents an integer of 1 to 30. ]

[In General Formula (c), R ₁ represents an alkyl or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

[In General Formula (d), R ₁ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic; , M and n each independently represent an integer of 1 to 50, and the sum of l, m and n represents 3 to 50. ]

[In the general formula (e), R _l represents an alkylene group having 1 to 4 carbon atoms, or an arylene group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, R ₂ is represents hydrogen or a methyl _group, R 3, _{R 4} and _{R 5} each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkanol group having 2 to 4 carbon atoms, _{a l} is Represents an alkylene group having 4 carbon atoms, and A ₂ represents an alkylene group having 2 to 3 carbon atoms. n represents an integer of 0 to 20, and m represents an integer of 1 to 50. ]   The tire rubber composition according to claim 1, wherein the surfactant is included in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component.   The tire rubber composition according to claim 1, wherein the tire rubber composition further comprises an amine-based antioxidant.   The tire rubber composition according to claim 1, wherein the tire rubber composition further comprises a wax.   The tire rubber composition according to claim 4, wherein the wax is microcrystalline or paraffin wax.   2. The tire rubber composition according to claim 1, wherein a cis 1,4-bond content of a conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is more than 92%.   The tire rubber composition according to claim 1, wherein the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer is 50 mol% or less. The conjugated diene compound-nonconjugated olefin copolymer has a content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of 5% or less. The tire rubber composition according to claim 1.   The rubber composition for tire according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a molecular weight distribution (Mw / Mn) of 10 or less.   The tire rubber composition according to claim 1, wherein the non-conjugated olefin is an acyclic olefin.   The tire rubber composition according to claim 1, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The tire rubber composition according to claim 10 or 11, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The tire rubber composition according to claim 12, wherein the non-conjugated olefin is ethylene.   The rubber composition for tire according to claim 1, wherein the conjugated diene compound has 4 to 8 carbon atoms.   The rubber composition for tire according to claim 14, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene. 2. The tire rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer is a butadiene-ethylene copolymer.   A pneumatic tire using the tire rubber composition according to any one of claims 1 to 16.