JP2013155259A - Rubber composition and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition excellent in weatherability (ozone resistance) and stain-proof property (discoloration resistance), and to provide a tire with sidewall excellent in weatherability (ozone resistance) and stain-proof property (discoloration resistance).SOLUTION: A rubber composition is produced by blending a rubber component containing a conjugated diene compound-nonconjugated olefin copolymer with a phenylenediamine-based antioxidant of ≥0.01 pt.mass but <1 pt.mass based on 100 pts.mass of the rubber component.

Description

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

  Conventionally, N- (1,3-dimethyl-butyl) -N′-phenyl-as an anti-aging agent is generally used in a sidewall rubber in order to ensure ozone resistance in a sidewall portion of a pneumatic tire. p-phenylenediamine alone or in combination with N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine and N, N′-diaryl-p-phenylenediamine Yes. However, by blending these compounds, when trying to obtain sufficient ozone crack resistance until the end of use of the tire, a relatively large amount (for example, a total of 4 parts by weight of anti-aging agent with respect to 100 parts by weight of the rubber component). It is necessary to blend the above compound). N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine is easily deposited on the surface due to external factors such as temperature, strain and ozone, and further undergoes an oxidation reaction. Since the color changes to brown or brown, there is a problem that it is not preferable in appearance when used in a large amount.

  To this problem, N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine, N, N′-di-secondary-butyl-p-phenylenediamine, and N- (methyl- A rubber composition containing at least two compounds selected from the group consisting of (heptyl) -N′-phenyl-p-phenylenediamine in an amount of 5 parts by mass or less with respect to 100 parts by mass of the rubber component. As a rubber composition containing 1.0 to 2.2 parts by mass of a phenylenediamine-based antioxidant for 100 parts by mass of a rubber component (for example, see Patent Document 1) (For example, refer to Patent Document 2).

Japanese Patent Application Laid-Open No. 11-172049 JP 2010-188955 A

  However, these conventional techniques have not yet achieved a high level of both weather resistance (ozone resistance) and contamination resistance (discoloration resistance), and further improvements have been desired.

  Accordingly, an object of the present invention is to provide a rubber composition having excellent weather resistance (ozone resistance) and stain resistance (discoloration resistance), and excellent weather resistance (ozone resistance) and stain resistance (discoloration resistance). It is to provide a tire with a side wall.

  As a result of intensive studies to achieve the above object, the present inventors have used a conjugated diene compound-nonconjugated olefin copolymer and a phenylenediamine-based anti-aging agent in combination to provide weather resistance (ozone resistance) and anti-resistance. It has been found that a rubber composition excellent in stain resistance (discoloration resistance) can be obtained.

That is, the rubber composition of the present invention includes a rubber component containing a conjugated diene compound-nonconjugated olefin copolymer and a phenylenediamine-based antioxidant, and the phenylenediamine is added to 100 parts by mass of the rubber component. It is characterized by blending a system anti-aging agent in an amount of 0.01 parts by mass or more and less than 1 part by mass.
When a conjugated diene compound-nonconjugated olefin copolymer is used as a rubber component and the phenylenediamine-based antioxidant is blended in an amount of 0.01 parts by weight or more and less than 1 part by weight with respect to 100 parts by weight of the rubber component, weather resistance (Ozone resistance) and stain resistance (discoloration resistance) can be improved.

Moreover, it is preferable that the rubber composition of this invention contains a wax further and 0.01 mass part-1 mass part of said wax was mix | blended with respect to 100 mass parts of said rubber components.
When 0.01 parts by mass to 1 part by mass of the wax is blended with respect to 100 parts by mass of the rubber component, weather resistance can be improved.

In the rubber composition of the present invention, the conjugated diene compound-nonconjugated olefin copolymer preferably has a conjugated diene compound-derived content of 30 mol% to 80 mol%. Moreover, it is preferable that the amount of cis-1,4 bonds in the conjugated diene compound-derived moiety is 50% or more.
By setting the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer to 30 mol% or more, workability can be sufficiently secured, and by setting it to 80 mol% or less, the nonconjugated olefin can be reduced. Since a certain amount is included, further improvement in weather resistance (ozone resistance) can be expected.
By setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to 50% or more, a low glass transition point (Tg) can be maintained, and thereby physical properties such as low-temperature characteristics are improved.

In the 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, and the non-conjugated olefin is an acyclic olefin. The number of carbon atoms is preferably 2 to 10, more preferably at least one selected from the group consisting of ethylene, propylene and 1-butene, and most preferably ethylene.
When the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene, copolymerization with the conjugated diene can be performed efficiently.

Moreover, the rubber composition of this invention WHEREIN: It is preferable that content of the said conjugated diene compound-nonconjugated olefin copolymer is 20-80 mass parts in 100 mass parts of rubber components.
By making content of the said conjugated diene compound-nonconjugated olefin copolymer into the said range, the balance of a dynamic magnification and crack growth property becomes good.

In the rubber composition of the present invention, the rubber component preferably further contains a diene rubber, and the content of the diene rubber is 10 parts by mass or more in 100 parts by mass of the rubber component. More preferred.
When the rubber component further contains a diene rubber, the compatibility with the conjugated diene compound-nonconjugated olefin copolymer is good, and crack growth can be improved.
When the content of the diene rubber is 10 parts by mass or more in 100 parts by mass of the rubber component, the crack growth resistance can be further improved.

Moreover, it is preferable that the rubber composition of the present invention is a rubber composition for a sidewall used for a sidewall member of a tire.
When the rubber composition of the present invention is used for a tire sidewall member, a sidewall member excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance) can be obtained.

The tire according to the present invention includes a sidewall using the rubber composition.
When a sidewall using the rubber composition is provided, a tire having a sidewall excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance) can be provided.

  According to the present invention, a rubber composition excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance), and excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance). A tire provided with a sidewall can be provided.

FIG. 1 is a cross-sectional view of a tire according to an embodiment of the present invention.

<Rubber composition>
Hereinafter, embodiments of the present invention will be specifically described.
The rubber composition of the present invention includes a rubber component and a phenylenediamine-based antiaging agent.

(Rubber component)
The rubber component constituting the rubber composition of the present invention contains a conjugated diene compound-nonconjugated olefin copolymer.

-Conjugated diene compound-nonconjugated olefin copolymer By having the conjugated diene compound-nonconjugated olefin copolymer, the double bond of the conjugated diene part (part derived from the conjugated diene compound) in the copolymer is a conjugated polymer. Therefore, the weather resistance (ozone resistance) of the rubber composition can be realized at a high level. On the other hand, contamination resistance (discoloration resistance), that is, the appearance when used in rubber products is not particularly adversely affected. Further, the crack growth resistance and fracture resistance can also be improved. Furthermore, since it becomes possible to hold | maintain a low glass transition point (Tg), a favorable low temperature characteristic is also realizable.

Here, the conjugated diene compound-nonconjugated olefin copolymer is a copolymer of a conjugated diene compound and a nonconjugated olefin, and includes a nonconjugated olefin together with the conjugated diene compound as a monomer unit component in the copolymer. .
By blending the conjugated diene compound-nonconjugated olefin copolymer into the rubber composition, the double bond of the conjugated diene part (part derived from the conjugated diene compound) in the copolymer is less than that of the conjugated polymer. , Ozone resistance is improved.
Here, the conjugated diene compound indicates a conjugated compound having two double bonds in the molecule, and the non-conjugated olefin is a non-conjugated olefin other than the conjugated diene compound and does not contain styrene. .
In addition, an olefin is an aliphatic unsaturated hydrocarbon and refers to a compound having one or more carbon-carbon double bonds.

There is no restriction | limiting in particular as content of the said conjugated diene compound origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 30 mol%-80 mol% are preferable.
By setting the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer to 30 mol% or more, workability can be sufficiently secured, and by setting it to 80 mol% or less, the nonconjugated olefin can be reduced. Since a certain amount is included, further improvement in weather resistance (ozone resistance) can be expected.

There is no restriction | limiting in particular as content of the said nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 20 mol%-70 mol% are preferable.
By making the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer 20 mol% or more, the weather resistance can be further improved, and by making the content 70 mol% or less, workability is improved. It is possible to maintain and improve crack growth resistance.

Further, the amount of cis-1,4 bonds in the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and can be appropriately selected according to the purpose. % Or more is preferable, more than 92% is particularly preferable, and 95% or more is most preferable.
By setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to 50% or more, a low glass transition point (Tg) can be maintained, and thereby physical properties such as low-temperature characteristics are improved. Furthermore, by making the amount of cis 1,4-bond of the conjugated diene compound-derived portion more than 92%, it becomes possible to improve crack growth resistance, weather resistance, and heat resistance, and by setting it to 95% or more. Further, the crack growth resistance, weather resistance, and heat resistance can be further improved.
The cis-1,4 bond amount is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer, by using a nonconjugated olefin as a monomer, excellent heat resistance and ozone resistance can be obtained, and it occupies the main chain of the copolymer. By reducing the double bond ratio and reducing the crystallinity, it becomes possible to increase the degree of design freedom as an elastomer. Moreover, as a nonconjugated olefin, it is preferable that it is an acyclic olefin, and it is preferable that carbon number of this nonconjugated olefin is 2-10.

Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with a conjugated diene can be performed efficiently. These non-conjugated olefins may be used alone or in combination of two or more.
In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

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

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

  In the conjugated diene compound-nonconjugated olefin copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, and is 10,000 to 1,000,000. It is more preferable, and it is especially preferable that it is 50,000-600,000. If the Mw exceeds 10,000,000, the moldability may be deteriorated.

  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).

The 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 is not particularly limited and depends on the purpose. However, it is preferably 5% or less, more preferably 3% or less, and particularly preferably 2.5% or less.
When the 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 is 5% or less, The weather resistance (ozone resistance) of the coalescence can be further improved.
On the other hand, the content of the conjugated diene compound in the conjugated diene compound-nonconjugated olefin copolymer-derived portion derived from the conjugated diene compound has a 1,2 adduct portion (including 3,4 adduct portion) content of 3% or less, The weather resistance (ozone resistance) of a copolymer can be further improved as it is 2.5% or less.
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 in the conjugated diene compound-derived portion has the same meaning as the 1,2-vinyl bond amount when the conjugated diene compound is butadiene. It is.

  The chain structure of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a block copolymer, a random copolymer, a taper copolymer, An alternating copolymer etc. are mentioned.

Block copolymer The structure of the block copolymer is (AB) _x , A- (BA) _x, and B- (AB) _x (where A is a non-conjugated olefin unit). B is a block portion consisting of monomer units of a conjugated diene compound, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multi-block copolymer.
When the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

・ Random copolymer When the conjugated diene compound-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, and the copolymer causes phase separation. Without observing the crystallization temperature derived from the block portion. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

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

-Alternating copolymer The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain of -ABABABAB- where A is a non-conjugated olefin and B is a conjugated diene compound) A polymer having a structure).

  In the present invention, when the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity. Since it is excellent in mechanical properties, in the case of a tapered copolymer, both flexibility and adhesiveness can be achieved. The copolymer is preferably at least one selected from a block copolymer and a tapered copolymer.

  The content of the conjugated diene compound-nonconjugated olefin copolymer is preferably in the range of 20 to 80 parts by mass in 100 parts by mass of the rubber component. This is because, when the content of the conjugated diene compound-nonconjugated olefin copolymer is within the above range, the balance between dynamic magnification and crack growth is improved. If the content of the conjugated diene compound-nonconjugated olefin copolymer is less than 20 parts by mass, the conjugated diene compound-nonconjugated olefin copolymer may be too small to obtain the desired crack growth resistance. On the other hand, if the content exceeds 80 parts by mass, the workability may be deteriorated.

-Manufacturing method of conjugated diene compound-nonconjugated olefin copolymer Next, the manufacturing method of said conjugated diene compound-nonconjugated olefin copolymer is demonstrated in detail. However, the manufacturing method described in detail below is merely an example.
The method for producing a conjugated diene compound-nonconjugated olefin copolymer is carried out in the presence of the following polymerization catalyst, first polymerization catalyst composition, second polymerization catalyst composition, or third polymerization catalyst composition. It is preferable to include a step of polymerizing a conjugated olefin and a conjugated diene compound. 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, hexane, cyclohexane, mixtures thereof etc. are mentioned.

（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）： First polymerization catalyst composition As the first polymerization catalyst composition (hereinafter also referred to as “first polymerization catalyst composition”), the following general formula (I):

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

（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）：

(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 ):

（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が挙げられる。

(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. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The first polymerization catalyst composition may further contain other components 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 above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid 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.

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

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

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

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

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

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a 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-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  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。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、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、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。 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.)
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.

（式中、Ｘ''はハライドを示す。）

(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.

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. 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 the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

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

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

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

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 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 amount of cis-1,4 bonds and the molecular weight of the resulting polymer can be increased.

Second Polymerization Catalyst Composition Next, the second polymerization catalyst composition (hereinafter also referred to as “second polymerization catalyst composition”) will be described.
As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. At least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds;
The polymerization catalyst composition containing is mentioned.
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 R1 and R2 are the same or different and have 1 to 10 carbon atoms. R ³ is a 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 1 in the periodic table. When the metal is selected from the group, a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and In the case where b is 1 and c is 0, and Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1].

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.
In the polymerization reaction system, the concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

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)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, 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 name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid 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. Among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

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

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

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

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

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 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 the general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). 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 represented by the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and 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, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Muzi hydride, isobutylaluminum 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.

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

(In the formula, 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 have 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
A polymer can be produced by using the metallocene polymerization catalyst. In addition, by using the above metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used during the synthesis of the polymer 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 polymer 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. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7X R _X or C ₉ H _11X 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 ^B is coordinated μ to M ¹及A ^l . Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

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

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、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 represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

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

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

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

  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. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. 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 third polymerization catalyst composition (hereinafter also referred to as “third polymerization catalyst composition”) includes the metallocene composite catalyst and a boron anion. Furthermore, it is preferable that other components contained in the polymerization catalyst composition containing a normal metallocene catalyst, for example, a co-catalyst and the like are included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the polymer can be arbitrarily controlled. It becomes.

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

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

-Polymerization step In the production of the conjugated diene compound-nonconjugated olefin copolymer in the rubber composition according to the present invention, when the polymerization catalyst or the polymerization catalyst composition is used, for example, a polymerization reaction using a conventional coordination ion polymerization catalyst. It can carry out similarly to the manufacturing method of the polymer by. Here, when the method for producing a copolymer uses the above-described polymerization catalyst composition, for example, (1) the configuration of the polymerization catalyst composition in a polymerization reaction system containing a non-conjugated olefin and a conjugated diene compound as monomers. The components may be provided separately and the polymerization catalyst composition may be prepared in the reaction system, or (2) a previously prepared polymerization catalyst composition 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 a nonconjugated olefin and a conjugated diene compound.

  In the method for producing a copolymer, the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.

  The polymerization reaction 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. Further, the pressure of the polymerization reaction is preferably in the range of 0.1 to 10 MPa in order to sufficiently incorporate the non-conjugated olefin and the conjugated diene compound into the polymerization reaction system. 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.

Further, when the non-conjugated olefin and the conjugated diene compound are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol / l) at the start of polymerization are expressed 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.

○ Diene rubber The rubber component preferably further contains a diene rubber. This is because the compatibility with the above-described conjugated diene compound-nonconjugated olefin copolymer is good and the crack growth resistance can be improved.
The diene rubber is not particularly limited and can be appropriately selected depending on the purpose. For example, natural rubber, various butadiene rubbers, isoprene rubber, and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, natural rubber is preferable because it can further improve crack growth resistance.

  Further, the content of the diene rubber is preferably 10 parts by mass or more and more preferably 20 parts by mass or more in 100 parts by mass of the rubber component. This is because the crack growth resistance can be improved, and if it is less than 10 parts by mass, the crack growth resistance may not be improved. The upper limit of the content of the diene rubber is not particularly limited, but is preferably 80 parts by mass or less in 100 parts by mass of the rubber component from the viewpoint of weather resistance.

  The rubber component can be contained in rubbers other than the conjugated diene compound-nonconjugated olefin copolymer and diene rubber described above. For example, non-diene rubber (butyl rubber (IIR), ethylene / propylene rubber (EPM, EPDM), urethane rubber (U), silicone rubber (Q), chlorosulfonated rubber (CSM), acrylic rubber (ACM), fluoro rubber (FKM), chlorosulfonated polyethylene, etc.) may be contained in small amounts.

(Phenylenediamine anti-aging agent)
The rubber composition of the present invention contains a phenylenediamine-based antioxidant.
Deterioration of the rubber composition can be prevented when the rubber composition contains a phenylenediamine-based antiaging agent. Further, the rubber composition contains a small amount of a phenylenediamine-based anti-aging agent (as described later, blended in an amount of 0.01 parts by weight or more and less than 1 part by weight with respect to 100 parts by weight of the rubber component), thereby providing weather resistance. (Ozone resistance) and stain resistance (discoloration resistance) can both be achieved.

The blending amount of the phenylenediamine-based antioxidant is required to be 0.01 parts by weight or more and less than 1 part by weight with respect to 100 parts by weight of the rubber component, and 0.1 parts by weight to 0.8 parts by weight. Is preferable, 0.2 mass part-0.5 mass part is more preferable.
By setting the blending amount of the phenylenediamine-based anti-aging agent to 0.01 parts by mass or more, it is possible to protect the rubber surface or internal physical properties, and by setting it to less than 1 part by mass, discoloration or contamination of the rubber surface. Can be prevented. Furthermore, by setting the blending amount of the phenylenediamine-based antioxidant to 0.1 parts by mass to 0.8 parts by mass, further protecting the rubber surface or internal physical properties and preventing discoloration or contamination of the rubber surface. By setting the content to 0.2 to 0.5 parts by mass, it is possible to further protect the rubber surface or internal properties and prevent discoloration or contamination of the rubber surface.

Ｎ−（１，３−ジメチルブチル）−Ｎ'−フェニル−ｐ−フェニレンジアミン（６Ｃ）として、大内新興化学工業（株）製のノクラック６Ｃ、住友化学工業（株）製のアンチゲン６Ｃ、フレキシス社製のサントフレックス１３、精工化学（株）製のオゾノン６Ｃ等が市販されている。 Examples of the phenylenediamine-based antioxidant include N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6C) having the following structural formula.

As N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6C), Nocrack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd. Antigen 6C manufactured by Sumitomo Chemical Co., Ltd., Flexis Santoflex 13 manufactured by the company, Ozonon 6C manufactured by Seiko Chemical Co., Ltd. are commercially available.

トリフェニレンジアミン（ＴＤ）：

ジフェニレンジアミン（Ｇ−１）：

などが挙げられる。 In addition, as other phenylenediamine anti-aging agent (A2),
Triphenylenediamine (DP):

Triphenylenediamine (TD):

Diphenylenediamine (G-1):

Etc.

  Among these phenylenediamine-based anti-aging agents, the solubility in rubber is moderate, and from the beginning to the middle of use, the rubber surface or the inside is resistant to ozone resistance, UV resistance, flex crack resistance, and oxidation resistance in a well-balanced manner. N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6C) is preferable because it can be improved.

パラフェニレンジアミン（７７ＰＤ、Ｎ，Ｎ'−ｂｉｓ（１，４−ｄｉｍｅｔｙｌｐｅｎｔｙｌ）−ｐ−ｐｈｅｎｙｌｅｎｅ ｄｉａｍｉｎｅ）：

を、Ｎ−（１，３−ジメチルブチル）−Ｎ'−フェニル−ｐ−フェニレンジアミン（６Ｃ）と混用することができる。 As a phenylenediamine-based anti-aging agent, a triphenylenediamine derivative (DTPD derivative, 1,4-benzodiamine, N, N′-mixed phenyl and tolyl derivatives):

Paraphenylenediamine (77PD, N, N′-bis (1,4-dimethylpentyl) -p-phenylenediamine):

Can be mixed with N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6C).

  A DTPD derivative is preferable because it has a higher molecular weight than N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6C), and has low migration. The use of 77PD can be expected to be resistant to ozone degradation.

(wax)
The rubber composition of the present invention may further contain a wax.
By including the wax, the weather resistance can be improved.

The blending amount of the wax is preferably 0.01 parts by mass to 1 part by mass, more preferably 0.1 parts by mass to 0.8 parts by mass, and 0.2 parts by mass to 0 parts by mass with respect to 100 parts by mass of the rubber component. .5 parts by mass is particularly preferred.
When the blending amount of the wax is 0.01 parts by mass or more, weather resistance can be improved, and when the amount is 1 part by mass or less, discoloration of the rubber surface can be prevented. Furthermore, by setting the blending amount of the wax to 0.1 parts by mass to 0.8 parts by mass, weather resistance can be further improved, discoloration of the rubber surface can be prevented, and 0.2 parts by mass By setting it as -0.5 mass part, a weather resistance can be improved further and it becomes possible to prevent discoloration of the rubber surface.

  Specific examples of the wax that can be blended in the rubber composition of the present invention include Sangite S manufactured by Seiko Chemical Co., Ltd., and Sannock manufactured by Ouchi Shinsei Chemical Co., Ltd.

(Other ingredients)
In addition, the rubber composition of the present invention is optionally provided with reinforcing fillers such as carbon black, silica, and clay; crosslinking agents; vulcanization accelerators; plasticizers; antioxidants; softeners such as aroma oils; Lubricants; UV absorbers; dispersants; compatibilizers; homogenizing agents; vulcanization accelerating aids such as stearic acid and zinc white; thermosetting resins;

The carbon black is not particularly limited, and those usually used may be adopted.
There is no restriction | limiting in particular as content of the said carbon black, Although it can select suitably according to the objective, 10 mass parts-80 mass parts are preferable with respect to 100 mass parts of rubber components. When the content of the carbon black is less than 10 parts by mass, normal physical properties and crack growth properties may be deteriorated. On the other hand, when it exceeds 80 mass parts, workability and dynamic magnification may be deteriorated.

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 and the like can be mentioned, and among these, sulfur-based crosslinking agents are more preferable as the rubber composition.
There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.3 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components. If the content of the cross-linking agent is 0.3 parts by mass or more, the cross-linking can surely proceed, and if it is 10 parts by mass or less, the cross-linking has progressed during kneading with some cross-linking agents. It is possible to prevent the physical properties of the vulcanized product from being deteriorated.

There is no restriction | limiting in particular as said sulfur type crosslinking agent, According to the objective, it can select suitably, For example, sulfur etc. are mentioned.
There is no restriction | limiting in particular as content of the said sulfur, Although it can select suitably according to the objective, 0.3 mass part-5 mass parts are preferable with respect to 100 mass parts of rubber components. If the sulfur content is less than 0.3 parts by mass, a sufficient vulcanization effect may not be obtained, and the target performance may not be achieved. If it exceeds 5 parts by mass, the rubber becomes brittle, and the rubber The fatigue performance may be reduced.

  The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include guanidine series such as diphenylguanidine, aldehyde-amine series, aldehyde-ammonia series, and thiazole series such as mercaptobenzothiazole. Compounds such as sulfenamides such as N, N′-dicyclohexyl-2-benzothiazolylsulfenamide, thiurams such as thiourea and tetramethylthiuram disulfide, dithiocarbamates, and xanthates can be used.

In addition, the rubber composition of this invention can be obtained by kneading said each component with kneading machines, such as a Banbury mixer, a kneader, a roll, an internal mixer, for example.
Moreover, it is preferable that the rubber composition of the present invention is a rubber composition for a sidewall used for a sidewall member of a tire.

  The sidewall using the rubber composition of the present invention can be produced, for example, by molding and processing the rubber composition of the present invention and then performing a vulcanization treatment. Vulcanization conditions can be selected as appropriate, but it is preferably carried out at a normal temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes.

  About the side wall using the rubber composition of the present invention, since the above-described rubber composition is used, the weather resistance (ozone resistance) and stain resistance (discoloration resistance) are improved as compared with the conventional side wall. Excellent.

<Tire>
The tire of the present invention includes the above-described sidewall.

  An embodiment of the tire of the present invention will be described with reference to FIG. The tire 100 includes a pair of bead cores 111 and 112, stiffeners 113 and 114, and a carcass ply 121. The stiffeners 113 and 114 extend outward from the bead cores 111 and 112 in the tire radial direction. The carcass ply 121 is folded back at the bead cores 111 and 112 outward in the tread width direction of the stiffeners 113 and 114 to form a horseshoe-shaped tire case shape. On the outer side in the tire radial direction of the carcass ply 121, a belt portion 115 including a plurality of belt layers is disposed.

  A tread portion 118 is disposed outside the belt portion 115 in the tire radial direction. In addition, an inner liner 130 is disposed inside the carcass ply 121 as an air permeation preventive layer.

  A sidewall portion 119 is formed on the outer side of the carcass ply 121 in the tire width direction. The sidewall portion 119 is formed using the rubber composition according to the present invention.

  As a method for manufacturing the tire, a conventional method can be used. For example, on a tire molding drum, members normally used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer containing unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing the green tire according to a conventional method.

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 Preparation of ethylene-butadiene copolymer (EBR1) After adding 2,000 g of a toluene solution containing 120 g (2.22 mol) of 1,3-butadiene to a sufficiently dry 4 L stainless steel reactor, ethylene was added. It was introduced at 1.72 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. , 28.5 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 2.00 mmol of diisobutylaluminum hydride were prepared and dissolved in 40 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 25.0 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at 50 ° C. for 90 minutes. After the polymerization, 5 ml of 2,2′methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) isopropanol solution (5 ml) was added to stop the reaction, and the copolymer was further added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer. The yield of the obtained copolymer EBR1 was 98 g.

Preparation Example 2 Preparation of Butadiene-Ethylene Copolymer (EBR2) After adding 2,000 g of a toluene solution containing 230 g (4.26 mol) of 1,3-butadiene to a sufficiently dry 4 L stainless steel reactor, ethylene was added. It was introduced at 1.72 MPa. Meanwhile, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 145 μmol, dimethyl 145 μmol of anilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 2.9 mmol of diisobutylaluminum hydride were charged and dissolved in 100 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 142 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at 60 ° C. for 60 minutes. After polymerization, 5 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a polymer. The yield of the obtained copolymer EBR2 was 248 g.

Preparation Example 3 Preparation of Butadiene-Ethylene Copolymer (EBR3) After adding 200 ml of a toluene solution containing 9.36 g (0.173 mol) of 1,3-butadiene to a well-dried 400 ml pressure-resistant glass reactor, ethylene was added. Was introduced at 0.6 MPa. On the other hand, (2-MeC ₉ H ₆ ) ₂ Sc (MeAlMe ₃ ) 21.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 21.0 μmol and 0.25 mmol of triisobutylaluminum 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, added to the monomer solution, and polymerized at 25 ° C. for 50 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a polymer. The yield of the obtained copolymer EBR3 was 9.30 g.

  About the ethylene-butadiene copolymer (EBR1-3) prepared as described above and the high cis-butadiene rubber (HCBR) (trade name: BR01, manufactured by JSR) obtained as a commercial product, the weight average molecular weight (Mw), The molecular weight distribution (Mw / Mn), ethylene content, 1,2-vinyl bond amount, and cis-1,4 bond amount were measured and evaluated by the following methods. The results are shown in Table 1.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMHHR-H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene, The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.
(2) Content of ethylene-derived portion The content (mol%) of the ethylene-derived portion in the ethylene-butadiene copolymer (EBR) is determined by 13C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). It calculated | required from the integral ratio of the whole ethylene coupling | bonding component (28.5-30.0ppm) and the whole butadiene coupling | bonding component (26.5-27.5ppm + 31.5-32.5ppm). Table 1 shows the ethylene content (mol%). In addition, the value which subtracted the content rate (mol%) of the obtained ethylene origin part from 100 mol% becomes the content rate (mol%) of a butadiene origin part (conjugated diene compound origin part).
(3) Microstructure (1,2-vinyl bond amount, cis-1,4 bond amount)
Microstructure (1,2-vinyl bond content) of butadiene moiety in ethylene-butadiene copolymer (EBR) and high cis-butadiene rubber (HCBR), ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard) : 6 ppm) from the integral ratio of the 1,2-vinyl bond component (5.0-5.1 ppm) to the total butadiene bond component (5-5.6 ppm), and the ethylene-butadiene copolymer (EBR) and high The microstructure (cis-1,4 bond amount) of the butadiene moiety in cis-butadiene rubber (HCBR) was determined by cis-1,4 by ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). Binding component (26.5-27.5 ppm) and total butadiene binding component (26.5-27.5 ppm + 31.5-32.5 ppm) It was obtained from the integral ratio of. The calculated values of 1,2-vinyl bond amount and cis-1,4 bond amount (%) are shown in Table 1.

(Examples 1-19 and Comparative Examples 1-7)
It adjusted with the compounding prescription shown in Tables 2-4 as a sample of the rubber composition of Examples 1-19 and Comparative Examples 1-7. Thereafter, the prepared rubber composition was vulcanized at 160 ° C. for 20 minutes to prepare a vulcanized rubber sample.

(Evaluation)
The weather resistance (ozone resistance) and stain resistance (discoloration resistance) of the rubber compositions and vulcanized rubber samples obtained in each of the examples and comparative examples were measured according to the following methods.

(1) Weather resistance (ozone resistance)
For the vulcanized rubber samples obtained in each Example and Comparative Example, a 20 mm × 100 mm × 1.0 mm test piece was stretched 50% and left in a constant temperature bath at 40 ° C. and an ozone concentration of 50 pphm, and cracked with the naked eye. Was measured, and indexed with Comparative Example 1 as 100. The evaluation results are shown in Tables 2-4. The larger the index value, the longer the time until cracks can be confirmed and the better the weather resistance.

(2) Stain resistance (discoloration resistance)
Contamination resistance was evaluated by measuring the color difference of the vulcanized rubber samples obtained in each Example and Comparative Example using a spectrocolorimeter CM-700d (manufactured by Konica Minolta Co., Ltd.). The evaluation results are shown in Tables 2-4. In addition, about evaluation of contamination resistance, it shows as a relative value when the contamination resistance of the comparative example 1 is set to 100, and the larger the numerical value, the higher the contamination resistance and the better the result.

* 1: RSS # 1
* 2: Carbon black, FEF, iodine adsorption amount = 43 g / kg, DBP oil absorption amount = 121 ml / 100 g, N ₂ SA (nitrogen adsorption specific surface area) = 42 m ² / g, “Asahi # 65” manufactured by Asahi Carbon Co., Ltd.
* 3: MXST made by Miyoshi Oil
* 4: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, knock rack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 5: N-phenyl-N'-1,2-isopropyl-p-phenylenediamine, knock rack 810-NA manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6: (Alpha-methylbenzyl) phenol Knock Rack SP manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 7: Sangite S manufactured by Seiko Chemical Co., Ltd.
* 8: N-cyclohexyl-2-benzothiazolylsulfenamide, Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 9: Dibenzothiazyl disulfide, Nouchira DM-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 10: Mikulon OT-20, manufactured by Shikoku Chemicals Co., Ltd.

  From Tables 2 to 4, the samples according to Examples 1 to 19 of the present invention are excellent in balance in terms of both weather resistance (ozone resistance) and stain resistance (discoloration resistance), while Comparative Example 1 It was found that the samples of ˜7 resulted in at least one item inferior to the examples.

  The present invention can provide a rubber composition excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance). By using the rubber composition for, for example, a tire sidewall, It is industrially useful in that it is excellent in weather resistance (ozone resistance) and stain resistance (discoloration resistance) as compared with the tires described above.

DESCRIPTION OF SYMBOLS 100 Tire 111,112 Bead core 113,114 Stiffener 115 Belt layer 118 Tread part 119 Side wall part 121 Carcass ply 130 Inner liner

Claims (14)

A rubber component containing a conjugated diene compound-nonconjugated olefin copolymer;
Including a phenylenediamine anti-aging agent,
A rubber composition comprising 0.01 part by mass or more and less than 1 part by mass of the phenylenediamine-based antioxidant for 100 parts by mass of the rubber component.   2. The rubber composition according to claim 1, further comprising 0.01 to 1 part by mass of the wax with respect to 100 parts by mass of the rubber component.   2. The rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a content of a conjugated diene compound-derived portion of 30 mol% to 80 mol%.   2. The rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a cis-1,4 bond content of a conjugated diene compound-derived portion of 50% or more.   2. The rubber composition according to claim 1, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The rubber composition according to claim 1, wherein the non-conjugated olefin is an acyclic olefin.   The rubber composition according to claim 1, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The rubber composition according to claim 7, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The rubber composition according to claim 8, wherein the non-conjugated olefin is ethylene.   2. The rubber composition according to claim 1, wherein the content of the conjugated diene compound-nonconjugated olefin copolymer is 20 to 80 parts by mass in 100 parts by mass of the rubber component.   The rubber composition according to claim 1, wherein the rubber component further contains a diene rubber.   The rubber composition according to claim 11, wherein the content of the diene rubber is 10 parts by mass or more in 100 parts by mass of the rubber component.   The rubber composition according to claim 1, wherein the rubber composition is a rubber composition for a sidewall used for a sidewall member of a tire.   A tire comprising a sidewall using the rubber composition according to claim 13.

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