JP5735886B2 - Rubber composition for rubber bearing coating and rubber for rubber bearing coating using the same - Google Patents

Description

  The present invention relates to a rubber composition for rubber bearing coating and a rubber for rubber bearing coating using the rubber composition, and more particularly, to improve the crack growth property, weather resistance and fracture resistance of the rubber for rubber bearing coating, and to sufficiently attenuate the rubber composition. The present invention relates to a rubber composition for covering a rubber bearing and a rubber for covering the rubber bearing using the rubber composition.

In recent years, when a building such as a building or a bridge is constructed, a seismic isolation structure is formed using a rubber bearing or the like in order to prevent damage due to vibration caused by an earthquake or the like.
A rubber bearing is a member that supports the load of the upper structure of a building such as a building or bridge, and is installed at the contact point between the upper structure and the lower structure of the building. This is to absorb the generated displacement of the upper structure and the lower structure with this rubber bearing. In general, a plurality of hard plates such as steel plates and a soft plate made of a rubber material having viscoelastic properties are alternately laminated, and the two are firmly bonded to improve load resistance and horizontal force. Can be handled by the elasticity of rubber.

However, with the tightening of increasing and seismic criteria disaster awareness recent earthquake, shear modulus G is high-performance rubber bearing in 0.3N / mm ² ~0.5N / mm ² as low modulus It came to be demanded.
In response to this requirement, studies have been made to obtain excellent elasticity and damping characteristics by adding a specific resin to the internal rubber used as the soft plate of the rubber bearing (see, for example, Patent Document 1). -For the rubber of the coating layer formed on the outer periphery of the rubber support body in order to improve the durability and weather resistance, the shear modulus G is still 0.6 N / in consideration of durability and workability during molding. In many cases, rubber with a size of mm ² or more is used. As a result, low elastic modulus rubber has come to be used as a soft plate for rubber bearings in order to meet stringent spring accuracy requirements associated with higher performance. There is a possibility that the rubber elastic modulus of the rubber will be raised and the performance of the entire rubber bearing will be lowered. This problem can be solved by applying a rubber having the same level of shear modulus as that of the soft plate of the rubber support body to the coating material. The actual situation is that there are still problems and the practical application is delayed. In other words, in addition to improving the appearance, durability, weather resistance, etc., the coating layer has an adhesive property with a rubber composition (internal rubber) used for the rubber support and a rubber composition used for the rubber support. Physical properties that do not impair the adhesiveness to (internal rubber) and the properties (rigidity and damping) of the rubber support are required.

In general, reducing the elastic modulus of rubber is effective by reducing the number of carbon components, using lower carbon, and increasing the amount of plasticizer and petroleum resin. Not only was it softened, but the tackiness was also greatly increased, resulting in a significant decrease in workability. In addition, when a coating material having a low elastic modulus is produced by the above method, there is a possibility that sufficient breaking strength may not be obtained, so that durability as a coating material may be insufficient. It has become a big issue.
Accordingly, it is desired to develop a rubber sheet for covering a rubber bearing that is excellent in workability before vulcanization and can provide a coating material for rubber bearing that has excellent fracture strength and low elastic modulus after vulcanization. It was rare.

  Therefore, from the viewpoint of durability and temperature dependency, use of natural rubber and a non-conjugated diene compound-non-conjugated olefin copolymer (EPDM) as a rubber component used in the coating layer has been studied (for example, patents). Reference 2). However, since the compatibility between the natural rubber and the non-conjugated diene compound-non-conjugated olefin copolymer (EPDM) is insufficient, there is still room for improvement in fracture resistance and crack growth resistance.

Japanese Patent No. 2570340 JP 2009-1603 A

  Accordingly, an object of the present invention is to improve the crack growth property, weather resistance, and fracture resistance of rubber for rubber bearing coating, and to provide a rubber composition for rubber bearing coating that can provide sufficient damping. It is to provide a rubber for covering a rubber bearing.

  The present inventors provide a conjugated diene polymer (A), a conjugated diene compound-nonconjugated olefin copolymer (B), and a nonconjugated diene compound-nonconjugated olefin copolymer containing ethylene-propylene-diene rubber. A rubber composition for rubber bearing coating containing a rubber component containing (C) and a resin (D), and containing 5 to 60 parts by mass of the resin with respect to 100 parts by mass of the rubber component, It has been found that the crack growth property, weather resistance, and fracture resistance of the rubber for covering a rubber support can be improved and sufficient damping properties can be obtained, and the present invention has been completed.

That is, the rubber composition for covering a rubber support of the present invention comprises a conjugated diene polymer (A), a conjugated diene compound-nonconjugated olefin copolymer (B), and a nonconjugated diene containing ethylene-propylene-diene rubber. A rubber composition for covering a rubber bearing, comprising a rubber component containing a compound-non-conjugated olefin copolymer (C) and a resin (D), wherein 5 parts by mass of the resin with respect to 100 parts by mass of the rubber component The conjugated diene compound-nonconjugated olefin copolymer (B) is a propylene-butadiene copolymer, containing ~ 60 parts by mass.

  In the rubber composition for covering a rubber support of the present invention, the proportion of the non-conjugated olefin-derived portion in the copolymer (B) is preferably 60 mol% or less.

  In the rubber composition for covering a rubber support of the present invention, the content of ethylene-propylene-diene rubber in the non-conjugated diene compound-non-conjugated olefin copolymer (C) is preferably 10% by mass or more.

  In the rubber composition for covering a rubber support according to the present invention, the copolymer (B) preferably has a polystyrene equivalent weight average molecular weight of 10,000 to 10,000,000.

  In the rubber composition for covering a rubber support of the present invention, the copolymer (B) preferably has a molecular weight distribution (Mw / Mn) of 10 or less.

  In the rubber composition for covering a rubber support of the present invention, the non-conjugated olefin in the copolymer (B) is preferably ethylene.

  In the rubber composition for covering a rubber support of the present invention, the resin (D) is a polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, aliphatic / alicyclic C5 petroleum resin, C5 / C9. It is preferably at least one selected from the group consisting of petroleum petroleum resins, C9 petroleum resins, terpene resins, and copolymers and modified products thereof.

  The rubber for covering a rubber bearing of the present invention is characterized by using the rubber composition for covering a rubber bearing of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition for rubber | gum support coating which can improve the crack growth property of the rubber | gum for rubber | gum support coating, a weather resistance, and fracture resistance, and can acquire sufficient damping property, and rubber | gum using the same Rubber for covering can be provided.

FIG. 1 is a cross-sectional view of an example of a rubber support using the rubber for covering a rubber support of the present invention as a coating layer.

(Rubber composition for rubber bearing coating)
The rubber composition for covering a rubber support of the present invention comprises at least a conjugated diene polymer (A), a conjugated diene compound-nonconjugated olefin copolymer (B), and a nonconjugated diene compound-nonconjugated olefin copolymer ( It comprises a rubber component containing C) and a resin (D), and further comprises carbon black, silica, wax, amide compound and other components as required.

<Rubber component>
The rubber component comprises at least a conjugated diene polymer (A), a conjugated diene compound-nonconjugated olefin copolymer (B), and a nonconjugated diene compound-nonconjugated olefin copolymer (C). If necessary, it further comprises other rubber components.

-Conjugated diene polymer (A)-
The conjugated diene polymer means a polymer (polymer) containing no non-conjugated olefin as a monomer unit component (part of copolymer). Styrene is not included in the non-conjugated olefin.
The conjugated diene polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include natural rubber (NR), various polybutadiene rubbers (BR), synthetic polyisoprene rubber (IR), and various styrenes. -Butadiene copolymer rubber (SBR), ethylene-propylene rubber (EPR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer Examples thereof include rubber (NBR) and chloroprene rubber. These may be used individually by 1 type and may use 2 or more types together.
Among these, natural rubber (NR), synthetic polyisoprene rubber (IR), various polybutadiene rubbers (BR), and styrene-butadiene copolymer rubber (SBR) are non-conjugated containing ethylene-propylene-diene rubber described later. The compatibility with the diene compound-nonconjugated olefin copolymer (C) is good, and this is preferable in that the fracture resistance and crack growth resistance can be improved.

The content of the conjugated diene polymer (A) in 100 parts by mass of the rubber component is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 90 parts by mass to 10 parts by mass, It is more preferable that it is 75 mass parts-25 mass parts.
When the content of the conjugated diene polymer (A) in 100 parts by mass of the rubber component is less than 10 parts by mass, the fracture resistance and workability may deteriorate, and when it exceeds 90 parts by mass, Weather resistance may deteriorate. On the other hand, when the content of the conjugated diene polymer (A) in 100 parts by mass of the rubber component is within the more preferable range, it is advantageous in terms of balance of performances.

-Conjugated diene compound-Non-conjugated olefin copolymer (B)-
The rubber composition of the present invention contains the conjugated diene compound-nonconjugated olefin copolymer (B), so that the conjugated diene portion of the conjugated diene compound-nonconjugated olefin copolymer (B) component is conjugated diene-based heavy. By improving the compatibility with the combined (A) component, and the non-conjugated olefin part of the (B) component improving the compatibility with the non-conjugated diene compound-non-conjugated olefin copolymer (C), fracture resistance And compatibility between the conjugated diene polymer (A) excellent in crack growth resistance and the nonconjugated diene compound-nonconjugated olefin copolymer (C) containing ethylene-propylene-diene rubber excellent in weather resistance. As a result of improvement, the weather resistance, fracture resistance and crack growth resistance of the rubber composition can be compatible at a high level. The conjugated diene compound-nonconjugated olefin copolymer (B) is a copolymer of a conjugated diene compound and a nonconjugated olefin, and contains a nonconjugated olefin as a monomer unit component in the copolymer.

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, 40 mol% or more is preferable.
When the content of the conjugated diene compound-derived portion is less than 40 mol%, the properties as an elastomer are low because it is close to plastic, and sufficient fracture resistance and crack resistance may not be obtained. Compatibility between the polymer (A) and the non-conjugated diene compound-non-conjugated olefin copolymer (C) containing ethylene-propylene-diene rubber is lowered, and the desired weather resistance, fracture resistance and crack growth resistance are reduced. This is because sex may not be obtained. From the viewpoint of obtaining better weather resistance, fracture resistance and crack growth resistance, the content of the conjugated diene compound-derived portion is preferably 60 mol% or more from the viewpoint of workability and bending fatigue. In addition, the said conjugated diene compound origin part means the part applicable to the conjugated diene compound used as a monomer in the said conjugated diene compound-nonconjugated olefin copolymer (A).
Moreover, as content of the said nonconjugated olefin origin part, it is more preferable that it is 60 mol% or less from the point of workability, and it is further more preferable that it is 40 mol% or less.

  In the conjugated diene compound-nonconjugated olefin copolymer (B), the weight average molecular weight (Mw) does not cause a problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. However, from the viewpoint of application to a polymer structural material, the polystyrene-equivalent weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000. Preferably, 50,000-600,000 is more preferable. 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).

In the conjugated diene compound-nonconjugated olefin copolymer (B), 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.
Using any of the specific examples of the conjugated diene compound described above, the block copolymer and the random copolymer can be prepared by the same mechanism.

  On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer (B), the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene compound, and has excellent heat resistance and the main chain of the copolymer. It is possible to increase the degree of design freedom as an elastomer by reducing the proportion of double bonds in the resin and reducing the crystallinity. As a kind of 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 the conjugated diene can be performed efficiently. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

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

The amount of cis-1,4 bonds in the conjugated diene compound-derived moiety in the conjugated diene compound-nonconjugated olefin copolymer (B) is not particularly limited and may be appropriately selected depending on the intended purpose. The above is preferable, 50% or more is more preferable, more than 92% is particularly preferable, and 95% or more is most preferable.
If the amount of cis 1,4-bond in the conjugated diene compound-derived portion is 25% or more, a low glass transition point (Tg) can be maintained, thereby improving crack growth resistance, wear resistance, etc. Physical properties are improved.
On the other hand, the crack growth resistance, weather resistance, and heat resistance can be improved by setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to more than 92%. Further, by making the cis 1,4-bond amount of the conjugated diene compound-derived portion 95% or more, 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.

The content of the conjugated diene compound-containing non-conjugated olefin copolymer (B) in the conjugated diene compound-derived portion is not particularly limited as the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound, Although it can select suitably according to the objective, 5% or less is preferable, 3% or less is more preferable, and 2.5% or less is especially preferable.
The conjugated diene compound-nonconjugated olefin copolymer (B) has a 1,2 adduct portion (including a 3,4 adduct portion) content of the conjugated diene compound in a portion derived from the conjugated diene compound of 5% or less. The weather resistance and ozone resistance of the copolymer can be further improved.
On the other hand, 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 2.5% or less. And the weather resistance and ozone resistance of the copolymer can be further improved.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound 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.

  There is no restriction | limiting in particular as a chain structure of the said conjugated diene compound-nonconjugated olefin copolymer (B), According to the objective, it can select suitably, For example, a block copolymer, a random copolymer, a taper copolymer. A polymer, an alternating copolymer, etc. are mentioned.

--Block copolymer--
The block copolymer has a structure of (AB) _x , A- (BA) _x and B- (AB) _x (where A is a monomer unit of a non-conjugated olefin. It is a block part, B is a block part 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 (B) is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and therefore mechanical properties such as breaking strength. Excellent. The block portion showing crystallinity can suppress a decrease in storage elastic modulus (G ′).

--Random copolymer--
When the conjugated diene compound-nonconjugated olefin copolymer (B) is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, so that the copolymer does not cause phase separation. The crystallization temperature derived from the block part is not observed. 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, a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. The block part is composed of at least one block part (also referred to as a block structure) and a random part (referred to as a random structure) in which monomer units of a conjugated diene compound and a nonconjugated olefin are irregularly arranged. It is a copolymer.
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.

--Alternate copolymer--
The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain structure of -ABABABAB-, where A is a non-conjugated olefin and B is a conjugated diene compound). It is a coalescence. In the case of the alternating copolymer, both flexibility and adhesiveness can be achieved.

  In the present invention, when the conjugated diene compound-nonconjugated olefin copolymer (B) is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity. Therefore, the copolymer is preferably at least one selected from a block copolymer and a tapered copolymer.

Moreover, there is no restriction | limiting in particular as content of the said conjugated diene compound-nonconjugated olefin copolymer (B) in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 10 mass parts It is preferable that it is -90 mass parts, and it is more preferable that it is 25 mass parts -75 mass parts.
When the content of the conjugated diene compound-nonconjugated olefin copolymer (B) in 100 parts by mass of the rubber component is less than 10 parts by mass, the weather resistance may deteriorate, and when the content exceeds 90 parts by mass. The fracture resistance and workability may deteriorate.
On the other hand, when the content of the conjugated diene compound-nonconjugated olefin copolymer (B) in 100 parts by mass of the rubber component is in the more preferable range, it is advantageous in terms of balance of performances.

--Conjugated diene compound-Method for producing non-conjugated olefin copolymer--
Next, a production method capable of producing the conjugated diene compound-nonconjugated olefin copolymer will be described in detail. However, the manufacturing method described in detail below is merely an example.
The conjugated diene compound-nonconjugated olefin copolymer includes a step of polymerizing a conjugated diene compound and a nonconjugated olefin in the presence of the polymerization catalyst or polymerization catalyst composition shown below.
As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  According to the above production method, except that the polymerization catalyst or the polymerization catalyst composition is used, the monomer conjugated diene compound and the non-conjugated olefin are produced in the same manner as in the production method of the polymer using the normal coordination ion polymerization catalyst. It can be copolymerized.

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

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

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物（以下、第一重合触媒組成物ともいう）が挙げられ、該重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。ここで、メタロセン錯体は、一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／Ｌの範囲であることが好ましい。 <First polymerization catalyst composition>
The polymerization catalyst composition includes the following general formula (I):

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

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

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex. In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the 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.

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

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

In the general formula (III), Cp ^R ′ having the 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.

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

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

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

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

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

The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

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

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. 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 copolymer can be increased.

<Second polymerization catalyst composition>
In addition, as the polymerization catalyst composition,
Component (a): 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): includes 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 Preferable examples include a polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (b-3) among organic compounds. Can
When the second polymerization catalyst composition contains at least one of an ionic compound (b-1) and a halogen compound (b-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is characterized by including.

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (a) and the component (b), where the polymerization catalyst composition is the ionic compound (b). -1) and at least one of the above halogen compounds (b-3),
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is necessary to include.
Since the ionic compound (b-1) and the halogen compound (b-3) have no 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 the said polymerization catalyst composition is a case where the said aluminoxane (b-2) is included, 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)
[Wherein, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3].

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

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 aluminoxane represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The content of the aluminoxane 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. By reacting with a certain 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 represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the component (c) described above can be used singly or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (a) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

<Polymerization catalyst and third polymerization catalyst composition>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].

［式中、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。 In a preferred example of the metallocene composite catalyst, the following formula (XV):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 1 to 20 carbon atoms. R ^a and R ^b are μ-coordinated to M ¹ and Al, and R ^c and R ^d each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by

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

<Metalocene composite catalyst>
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.] By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. Is demonstrated.

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

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

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

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

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

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

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

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

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

（式中、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.

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

On the other hand, the organoaluminum compound used 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 polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. Become.

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

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

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

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

  In the method for producing a copolymer, as described above, polymerization is carried out in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. be able to. Here, in the copolymer production method, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The polymerization catalyst composition may be used in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

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

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

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

In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) means 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.

  Further, even if the first polymerization catalyst composition or the second polymerization catalyst composition is not used, that is, when a normal coordination ion polymerization catalyst is used, the monomer into the polymerization reaction system The copolymer can be produced by adjusting the charging method. That is, the second production method of the copolymer is characterized by controlling the chain structure of the copolymer by controlling the introduction of the conjugated diene compound in the presence of the non-conjugated olefin, The arrangement of the monomer units in the copolymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene compound and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example.

  Here, the charging method of the conjugated diene compound may be either continuous charging or split charging, and further, continuous charging and split charging may be combined. Moreover, continuous injection means adding for a fixed time at a fixed addition rate, for example.

  Specifically, the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin. As a result, it is possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.

  For example, when the copolymer is produced by the second production method, it is effective to continuously add a conjugated diene compound in the presence of the non-conjugated olefin to the polymerization reaction system in which the polymerization of the non-conjugated olefin has been started in advance. It becomes. In particular, when a multi-block copolymer is produced by the second production method, “a non-conjugated olefin is polymerized in a polymerization reaction system, and then the conjugated diene compound is reacted in the presence of the non-conjugated olefin. It is effective to repeat the operation of “continuous charging into the system” twice or more.

  The second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above. For example, the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.

  In the second production method, it is necessary to control the input of the conjugated diene compound. Specifically, it is preferable to control the input amount of the conjugated diene compound and the input frequency of the conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly added, the number of times the conjugated diene compound is added is not particularly limited, but is preferably in the range of 1 to 5 times. If the conjugated diene compound is charged too many times, it may be difficult to distinguish between a block copolymer and a random copolymer.

  In the second production method, since it is necessary that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged, the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

<Non-conjugated diene compound-non-conjugated olefin copolymer (C)>
The rubber composition of the present invention contains a non-conjugated diene compound-non-conjugated olefin copolymer (C) containing ethylene-propylene-diene rubber (EPDM). Excellent weather resistance can be realized by EPDM contained in the non-conjugated diene compound-non-conjugated olefin copolymer (C).

  The non-conjugated diene compound-non-conjugated olefin copolymer (C) is a copolymer of a non-conjugated diene compound and a non-conjugated olefin, and includes a non-conjugated olefin as a monomer unit component in the copolymer. Furthermore, the diene content of the nonconjugated diene compound-nonconjugated olefin copolymer (C) is 10% or less.

  Here, regarding the EPDM contained in the non-conjugated diene compound-non-conjugated olefin copolymer (C), a small amount of the third component is added to the ethylene propylene rubber (EPM) which is a copolymer of ethylene and propylene. Introduced and provided with a double bond in the main chain. There are various synthetic rubbers depending on the type and amount of the third component, and typical third components include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP). ) And the like. Regarding the properties of the EPDM, in addition to the above weather resistance, it is excellent in aging resistance, cold resistance, solvent resistance and the like.

  Moreover, it is preferable that content of EPDM in the said nonconjugated diene compound-nonconjugated olefin copolymer (C) is 10 mass% or more. This is because if the content is less than 10% by mass, the EPDM content is too small, and sufficient weather resistance may not be ensured.

In addition, about the other conditions (a conjugated diene compound, nonconjugated olefin copolymers other than EPDM, a manufacturing method, etc.) of the said nonconjugated diene compound-nonconjugated olefin copolymer (C), the said conjugated diene compound-nonconjugated. It is the same as that of the olefin copolymer (A).

There is no restriction | limiting in particular as content of the said nonconjugated diene compound-nonconjugated olefin copolymer (C) in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 10 mass parts- It is preferable that it is 30 mass parts.
When the content of the non-conjugated diene compound-non-conjugated olefin copolymer (C) in 100 parts by mass of the rubber component is less than 10 parts by mass, sufficient weather resistance may not be obtained. If it exceeds the part, sufficient crack growth resistance may not be obtained. On the other hand, when the content of the non-conjugated diene compound-non-conjugated olefin copolymer (C) in 100 parts by mass of the rubber component is within a more preferable range, it is advantageous in terms of weather resistance.

<Mass ratio of (A), (B) and (C)>
The mass ratio of the conjugated diene polymer (A), the conjugated diene compound-nonconjugated olefin copolymer (B), and the nonconjugated diene compound-nonconjugated olefin copolymer (C) is particularly limited. However, it is preferably 80:10:10 to 10:60:30 from the viewpoint that the weather resistance, fracture resistance and workability can be exhibited in a balanced manner.
When the mass ratio of the conjugated diene compound-nonconjugated olefin copolymer (B) is less than 10%, the compatibilizing effect may not be sufficiently obtained, and the nonconjugated diene compound-nonconjugated olefin copolymer If the mass ratio of (C) is less than 10%, the weather resistance effect may not be sufficiently obtained, and if the mass ratio of the non-conjugated diene compound-non-conjugated olefin copolymer (C) exceeds 30%. There is a possibility that the effect of crack growth resistance cannot be sufficiently obtained.

-Other rubber components-
There is no restriction | limiting in particular as said other rubber | gum, According to the objective, it can select suitably, For example, polysulfide rubber, silicone rubber, fluororubber, urethane rubber etc. are mentioned. About another rubber component, it may be used individually by 1 type and may use 2 or more types together.

<Resin (D)>
The rubber composition used in the present invention may contain various resins (D) for imparting damping characteristics together with the rubber component described above.
The resin (D) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, and aliphatic / alicyclic C5. -Based petroleum resin, C5 / C9-based petroleum resin, C9-based petroleum resin, terpene resin, and copolymers and modified products thereof. The said resin (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

-Polyester polyol resin-
There is no restriction | limiting in particular as said polyester polyol resin, According to the objective, it can select suitably, For example, it is a polycondensate of polyhydric carboxylic acid and polyhydric alcohol, Comprising: Two hydroxyl groups in 1 molecule Examples thereof include the resins described above.
A specific example of the polycondensate of the polyvalent carboxylic acid and the polyhydric alcohol having two or more hydroxyl groups in one molecule is not particularly limited and may be appropriately selected depending on the purpose. For example, both ends obtained by condensing dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and dihydric alcohols such as mono, di, triethylene glycol, mono, and dipropylene glycol And polyester diol having a hydroxyl group.

-Dicyclopentadiene resin-
The dicyclopentadiene resin is a resin obtained by polymerizing dicyclopentadiene using a Friedel-Craft catalyst such as AlCl ₃ or BF ₃ .
Specific examples of commercial products of the dicyclopentadiene resin include Quinton 1920 (manufactured by Zeon Corporation, high molecular weight), Marcaretz M-890A (manufactured by Maruzen Petrochemical Co., Ltd., low molecular weight), and the like.

-Rosin resin-
The rosin resin is a resin contained in raw pine or tall oil or the like, and three types of gum rosin, tall oil rosin and wood rosin are known.
The modified product of the rosin resin is not particularly limited and may be appropriately selected depending on the intended purpose. Polymerized rosin; glycerin ester rosin, partially hydrogenated rosin, fully hydrogenated rosin, polymerized rosin; pentaerythritol ester rosin , Partially hydrogenated rosin, polymerized rosin; and the like.

-Phenolic resin-
There is no restriction | limiting in particular as said phenol resin, According to the objective, it can select suitably, For example, p-tert- butylphenol acetylene resin, phenol-formaldehyde resin, etc. are mentioned.

-Xylene resin-
There is no restriction | limiting in particular as said xylene resin, According to the objective, it can select suitably, For example, the resin obtained by making m-xylene and formaldehyde react in presence of an acidic catalyst, etc. are mentioned.

-Aliphatic and alicyclic C5 petroleum resin-
The aliphatic / alicyclic C5-based petroleum resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cyclopentadiene, dicyclopentadiene (cyclopentadiene dimer is C10, C5 fractions), and copolymer resins made from C5 fractions such as isoprene, 1,3-pentadiene, 1-pentene, and 2-pentene.

-C5 / C9 petroleum resin-
There is no restriction | limiting in particular as said C5 / C9 type petroleum resin, According to the objective, it can select suitably, For example, C9 type | system | groups, such as said C5 type | system | group fraction, indene, styrene, methylindene, (alpha) -methylstyrene, etc. Examples thereof include a copolymer resin made from a mixture with a fraction.

-C9 petroleum resin-
There is no restriction | limiting in particular as said C9 type petroleum resin, According to the objective, it can select suitably, For example, the copolymer resin etc. which use the said C9 type fraction as a raw material etc. are mentioned.

-Terpene resin-
There is no restriction | limiting in particular as said terpene resin, According to the objective, it can select suitably, For example, (beta) -pinene resin, (alpha) -pinene resin, terpene phenol resin etc. can be mentioned.

In addition, the above aliphatic / alicyclic C5 petroleum resins, C5 / C9 petroleum resins, C9 petroleum resins, and petroleum resins into which polar groups formed by modifying these hydrogenated resins are introduced can also be used. .
There is no restriction | limiting in particular as said polar group introduce | transduced, According to the objective, it can select suitably, A phenolic hydroxyl group, alcoholic hydroxyl group, a carboxy group, etc. are mentioned.
The amount of the polar group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. However, the hydroxyl value (mgKOH / g) is preferably 2 to 400, more preferably 10 to 300. The amount of polar groups present in the petroleum resin can be measured by the method described in JIS K0070.

  In the rubber composition used in the present invention, the weight average molecular weight (Mw) of the resin (D) used in combination with the rubber component is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferable, and 500 to 3000 is more preferable. When the weight average molecular weight is within this range, sufficient attenuation can be obtained.

The content of the resin (D) is not particularly limited as long as it is 5 to 60 parts by mass with respect to 100 parts by mass of the rubber component, and can be appropriately selected according to the purpose. Part-40 mass parts is preferable.
When the content of the resin (D) in 100 parts by mass of the rubber component is 5 parts by mass to 60 parts by mass, sufficient attenuation can be obtained, and deterioration of mechanical properties and workability can be prevented.

<Carbon black>
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Nitrogen adsorption specific surface area of the carbon black (N ₂ SA, JIS K 6217-2: 2
As it conforms to 001) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably ^{20m 2 / g~100m 2 / g,} 35m 2 / g~80m 2 / g is more preferable. Wherein the carbon black nitrogen adsorption specific surface area (N ₂ SA) is less than 20 m ² / g, low durability of the resulting rubber, may not sufficiently crack growth resistance is obtained, 100 m ² /
When it exceeds g, low loss property falls and workability | operativity may be bad.
The nitrogen adsorption specific surface area (N ₂ SA) is, for example, JIS K 6217-2: 2.
It can be measured according to 001.
There is no restriction | limiting in particular as content of carbon black with respect to 100 mass parts of said rubber components, Although it can select suitably according to the objective, 10 mass parts-70 mass parts are preferable, 2
0 to 60 parts by mass is more preferable. When the carbon black content is less than 10 parts by mass, the reinforcing property may be insufficient and the fracture resistance may deteriorate, and when it exceeds 70 parts by mass,
Workability and low loss property may be deteriorated. Meanwhile, the carbon black content is
Within the more preferable range, it is advantageous in terms of the balance of each performance.

<Silica>
By using the silica in combination with the carbon black, an increase in elastic modulus can be suppressed while maintaining the fracture characteristics of rubber.
There is no restriction | limiting in particular as said silica, Although what is normally used in this field | area can be used, Hydrophobized silica is preferable.
As the hydrophobic treated silica is not particularly limited and may be appropriately selected depending on the purpose, the nitrogen adsorption specific surface area (BET method) is 150m ² / g~500m ² / g (preferably 150～350M ² / g with respect to wet silica 100 parts by weight in the range of), kinematic viscosity ^{10 -6 m 2 / s~1m 2 /} s silicone oil 0.1 part by weight to 50 parts by mass to surface treatment in the range of What is obtained is preferable.
If the specific surface area of the wet silica is less than 150 m ² / g, desired fracture characteristics may not be obtained, and if it exceeds 500 m ² / g, dispersibility in the rubber component may be reduced. In addition, there is no restriction | limiting in particular as DBP absorption amount of the said silica, Although it can select suitably according to the objective, 150 ml / 100g-350 ml / 100g are preferable.

There is no restriction | limiting in particular as addition amount of the said silica, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 5 mass parts-10 masses. Part is more preferred.
If the amount of silica added exceeds 10 parts by mass, it may be difficult to obtain the desired shear modulus G, and if it is less than 1 part by mass, the effect on fracture characteristics may not be obtained.
In the present invention, when the silane is kneaded with the rubber component, a known silane coupling agent may be added as appropriate, thereby improving the dispersibility in the rubber component.

<Wax, Amide Compound>
The wax or amide compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include waxes such as paraffin wax and microcrystalline wax; amides such as stearic acid amide, oleic acid amide and erucic acid amide. Compound; and the like. The said resin wax and an amide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, microcrystalline wax and erucic acid amide are preferable in that the adhesiveness of the rubber sheet can be reduced and the molding workability when covering the rubber support can be improved.
The addition amount of the wax and amide compound is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 2 parts by mass with respect to 100 parts by mass of the rubber component. 0.5 mass part-1 mass part are more preferable.
If the added amount of the wax or amide compound is less than 0.5 parts by mass, the desired processability improving effect may not be obtained. If the amount exceeds 2 parts by mass, the appearance may be deteriorated. .

<Other ingredients>
As other components, as long as the object of the present invention is not impaired, known vulcanizing agents, vulcanization accelerators, anti-aging agents, zinc white (ZnO), waxes, antioxidants, fillers, foaming agents, Additives such as plasticizers, lubricants, tackifiers, ultraviolet absorbers, fatty acids, anti-aging agents, softeners, and retarders can be appropriately blended.

-Plasticizer-
The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include process oils such as aromatic oils, naphthenic oils and paraffin oils; vegetable oils such as palm oils; synthesis of alkylbenzene oils and the like Oil; and the like.
Among these, process oil is preferable, and paraffin oil is particularly preferable.
There is no restriction | limiting in particular as addition amount of the said plasticizer, Although it can select suitably according to the objective, 20 mass parts-50 mass parts are preferable with respect to 100 mass parts of rubber components.

-Vulcanizing agent-
There is no restriction | limiting in particular as said vulcanizing agent, According to the objective, it can select suitably, For example, sulfur etc. are mentioned.
There is no restriction | limiting in particular as addition amount of the said vulcanizing agent, Although it can select suitably according to the objective, 0.5 mass part-3 mass parts are preferable with respect to 100 mass parts of said rubber components.
When the addition amount of the vulcanizing agent is less than 0.5 parts by mass, the fracture characteristics of the rubber composition may be deteriorated, and when it exceeds 3 parts by mass, a desired elastic modulus may not be obtained. .

-Vulcanization accelerator-
The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include CBS (N-cyclohexyl-2-benzothiazylsulfenamide) and TBBS (Nt-butyl- 2-benzothiazylsulfenamide), sulfenamide-based vulcanization accelerators such as TBSI (Nt-butyl-2-benzothiazylsulfenimide); guanidine-based additions such as DPG (diphenylguanidine) And sulfur accelerators; thiuram vulcanization accelerators such as tetraoctyl thiuram disulfide and tetrabenzyl thiuram disulfide; vulcanization accelerators such as zinc dialkyldithiophosphate; and the like.
There is no restriction | limiting in particular as addition amount of the said vulcanization accelerator, Although it can select suitably according to the objective, 1.5 mass parts-3.5 mass parts are preferable with respect to 100 mass parts of rubber components.

-Filler-
The filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic fillers such as white carbon, fine particle magnesium silicate, heavy calcium carbonate, magnesium carbonate, clay and talc, Examples thereof include organic fillers such as styrene resin, coumarone indene resin, phenol resin, lignin, modified melamine resin, and rosin derivative. There is no restriction | limiting in particular as addition amount of the said filler, Although it can select suitably according to the objective, 10 mass parts-50 mass parts are preferable with respect to 100 mass parts of rubber components.

-Anti-aging agent-
There is no restriction | limiting in particular as said anti-aging agent, According to the objective, it can select suitably, For example, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine (6C), N Known amine-based or phenol-based anti-aging agents such as -phenyl-N'-isopropyl-p-phenylenediamine (3C) and 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD) Can be mentioned.
There is no restriction | limiting in particular as content of the said anti-aging agent, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass. Part to 10 parts by mass is more preferable.

-Softener-
There is no restriction | limiting in particular as said softener, According to the objective, it can select suitably, For example, hydrocarbon resins, such as an aromatic modified terpene hydrocarbon resin, etc. are mentioned.
There is no restriction | limiting in particular as content of the said fatty acid, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of rubber components.

-Fatty acid-
There is no restriction | limiting in particular as said fatty acid, According to the objective, it can select suitably, For example, a stearic acid etc. are mentioned.
There is no restriction | limiting in particular as content of the said fatty acid, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass part- 5 parts by mass is more preferable.

-Retarder-
There is no restriction | limiting in particular as said retarder, According to the objective, it can select suitably, For example, N- (cyclohexylthio) phthalimide (PVI) etc. are mentioned.
There is no restriction | limiting in particular as content of the said retarder, Although it can select suitably according to the objective, 0.1 mass part-0.5 mass part are preferable with respect to 100 mass parts of rubber components.

-Zinc oxide-
There is no restriction | limiting in particular as content of the said zinc oxide, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, 1 mass part -5 mass parts is more preferable.

<Method for Producing Rubber Composition for Covering Rubber Bearing>
The method for producing the rubber composition for covering a rubber support according to the present invention is not particularly limited and can be appropriately selected according to the purpose. You may mix and knead | mix each component in a stage or 3 steps.
In the kneading, a kneader such as a roll, an internal mixer, a Banbury rotor, or the like can be used.

(Rubber for rubber bearing coating)
The rubber for covering a rubber bearing of the present invention is characterized by using the rubber composition for covering a rubber bearing of the present invention.
The shear modulus G after vulcanization of the rubber bearing coating rubber, s not particularly limited and may be appropriately selected depending on the ^{purpose, 0.3N / mm 2 ~1.0N / mm} 2 is ^{preferably, 0.35N / mm 2 ~0.75N / mm} 2 is more preferable.
There is no restriction | limiting in particular as the fracture strength after vulcanization | cure of the said rubber for rubber | gum support coating | cover, Although it can select suitably according to the objective, 12 Mpa or more is preferable and 14 Mpa or more is more preferable.

<Production method of rubber for rubber bearing coating>
When the sheet-like rubber support covering rubber (rubber sheet) is formed from the rubber support covering rubber composition, a known forming machine such as an extrusion molding machine or a press machine may be used.
A rubber bearing excellent not only in appearance but also in durability, weather resistance, and the like can be obtained by winding the rubber sheet around the outer periphery of the rubber bearing body, coating the rubber sheet, and then curing and curing. The vulcanization conditions at this time are not particularly limited, but usually vulcanization conditions of 120 to 160 ° C. can be employed.
For example, as shown in FIG. 1, a rubber bearing body 20 in which the rubber for covering a rubber bearing according to the present invention is used includes a soft plate 11 made of rubber having viscoelastic properties, and a hard plate 12 having rigidity such as a steel plate. The mounting surface plates 4 and 5 are provided on the upper and lower surfaces of the rubber laminate 13 formed by alternately laminating and. Thus, the rubber laminate 13 is covered with the covering layer 14.
The rubber for covering rubber support according to the present invention is used for the coating layer 14, for example.

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. Hereinafter, the descriptions of “Example 1”, “Example 2”, “Example 3”, “Example 5”, and “Example 8” are “Reference Example 1” and “Reference Example 2”, respectively. ”,“ Reference Example 3 ”,“ Reference Example 5 ”, and“ Reference Example 8 ”.

(Evaluation)
According to the following methods, weather resistance (ozone resistance), fracture resistance, crack growth resistance (index), equivalent attenuation of rubber compositions and vulcanized rubber samples obtained in each of Examples and Comparative Examples to be described later The coefficient, Tb (tensile breaking stress) and Eb (tensile breaking elongation) were measured. Moreover, the analysis method of a conjugated diene compound-nonconjugated olefin copolymer is shown below.

(1) Weather resistance (ozone resistance)
About the sample of the vulcanized rubber obtained by each Example and the comparative example, ozone resistance was measured according to JISK6259. While giving 30% dynamic stretching of the strip-shaped test piece,
The sample was exposed under an ozone concentration of 50 pphm, and the state of the sample (presence of cracks) after 24 hours was judged visually. The results are shown in Tables 1 and 2.
In Tables 1 and 2, ◯ indicates “no crack” and Δ indicates “crack”.

(2) Fracture resistance (Tb (tensile rupture stress) and Eb (tensile rupture elongation))
About the sample of the vulcanized rubber obtained in each Example and Comparative Example, according to JIS K 6251, the strength at break (Tb (tensile rupture stress)) and the elongation at break (Eb (tensile rupture elongation) at room temperature by a tensile test. ) Was measured, and indexed with Comparative Example 1 as 100. The results are shown in Tables 1 and 2.
In Table 1 and 2, it displays by the index when the comparative example 1 is set to 100, and it shows that destruction resistance is so favorable that a numerical value is large.

(3) Crack growth resistance (constant strain)
About the vulcanized rubber samples obtained in each of the examples and comparative examples, a 0.5 mm crack was made in the center of the JIS No. 3 test piece, and fatigue was repeatedly given at a constant strain of 0 to 100% at room temperature. The number of times until the measurement was measured and evaluated.
In Table 1 and 2, it displays by the index when the comparative example 1 is set to 100, and it shows that crack growth resistance (constant strain) is so favorable that an index value is large.

(4) Equivalent damping coefficient (Heq 100%)
One rectangular rubber sheet (thickness 2 mm) punched into a 25 mm × 25 mm square was produced from the vulcanized rubber samples obtained in the examples and comparative examples. The rectangular rubber sheet was sandwiched between two iron plates (25 mm × 60 mm × thickness 2.3 mm) coated with an adhesive so as to have a crank shape in cross section. In this way, vulcanization was performed in a state where the iron plate and the surface of the rubber sheet in contact with the iron plate were bonded, and the measurement was obtained by bonding the iron plate and the rubber sheet surface. The obtained measurement sample was placed in a spring stiffness and loss energy measuring device [manufactured by Kakinomiya Seisakusho, model “EFH-26-8-10”]. Two steel plates were applied to the outer and inner sides of the rectangular rubber sheet at a frequency of 0.2 Hz by changing the shear rate in the order of the first and second times described below to apply shear force. At the same shear rate, a shear force was applied three times.
1st: 50% → 100% → 200% → 300%
Second time: 50%-100%->200%-> 300%
Then, at each shear rate, the measured value when the first shear force was applied (third time) and the measured value when the second shear force was applied (third time) were averaged to calculate Heq 100%.
In Table 1 and Table 2, it displays by the index when the comparative example 1 is set to 100, and it shows that attenuation property is so high that an index value is large.

<Method for analyzing copolymer>
-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of copolymer-
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.

(Preparation Example 1)
-Preparation of butadiene-ethylene 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 introduced at 1.72 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 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 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, Anilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 145 μmol 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 sufficiently dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.6 MPa. On the other hand, in a glove box under a nitrogen atmosphere, (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.

(Preparation Example 4)
-Preparation of ethylene-butadiene copolymer (EBR4)-
After adding 2,000 g of a toluene solution containing 80 g (1.48 mol) of 1,3-butadiene to a sufficiently dry 4 L stainless steel reactor, ethylene was introduced at 1.72 MPa. On the other hand, in a glove box under a nitrogen atmosphere, 28.5 μmol of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) 2GdN (SiHMe ₂ ) ₂ ] in a glass container. Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 28.5 μmol and 2.00 mmol of diisobutylaluminum hydride were charged 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 80 ° C. for 90 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 EBR4 was 78 g.

(Preparation Example 5)
-Preparation of propylene-butadiene copolymer (PBR)-
A glass bottle with a rubber stopper having a volume of 200 ml was dried and purged with nitrogen, and 0.05 mol of VOCl ₃ (oxovanadium trichloride), 0.10 mol of neopentyl alcohol and toluene were added. Thereafter, the hydrochloric acid generated while bubbling with nitrogen was pierced and removed to obtain a toluene solution of dineopentoxyoxovanadium chloride.
A glass bottle with a rubber stopper having a volume of about 1 liter was dried and purged with nitrogen, and 250 g of a toluene solution (17.5 wt%) of butadiene that had been purified by drying was added. Next, this glass bottle was cooled to −78 ° C., and 50 g of propylene gas was fed. 2.81 mmol of triisobutylaluminum (normal hexane solution 1 mol / L) was added, and the mixture was stirred and allowed to stand for about 10 minutes. Then, 0.47 mmol of the vanadium solution prepared above was added to initiate the polymerization, and the temperature was -78 ° C. The reaction was performed for 4 hours. Thereafter, the reaction was stopped by adding 2 ml of a 5% isopropanol solution of the antioxidant 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) at 50 ° C., and After reprecipitating in isopropanol containing a small amount of NS-5, drying on a drum gives a propylene-butadiene copolymer (PBR) corresponding to the conjugated diene compound-nonconjugated olefin copolymer (A). It was. The yield of the obtained copolymer PBR was about 70% by mass, the diene content was 50 mol%, and the weight average molecular weight (Mw) was 250,000.

(Preparation Example 6)
-Preparation of butene-butadiene copolymer (BBR)-
A glass bottle with a rubber stopper having a volume of 200 ml was dried and purged with nitrogen, and 0.05 mol of VOCl ₃ (oxovanadium trichloride), 0.10 mol of neopentyl alcohol and toluene were added. Thereafter, the hydrochloric acid generated while bubbling with nitrogen was pierced and removed to obtain a toluene solution of dineopentoxyoxovanadium chloride.
A glass bottle with a rubber stopper having a volume of about 1 liter was dried and purged with nitrogen, and 250 g of a toluene solution (17.5 wt%) of butadiene that had been purified by drying was added. Next, this glass bottle was cooled to −78 ° C., and 66 g of butene gas was fed. 2.81 mmol of triisobutylaluminum (normal hexane solution 1 mol / L) was added, and the mixture was stirred and allowed to stand for about 10 minutes. Then, 0.47 mmol of the vanadium solution prepared above was added to initiate the polymerization, and the temperature was -78 ° C. The reaction was performed for 12 hours. Thereafter, the reaction was stopped by adding 2 ml of a 5% isopropanol solution of the antioxidant 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) at 50 ° C., and After reprecipitation in isopropanol containing a small amount of NS-5, the product is dried on a drum to obtain a butene-butadiene copolymer (BBR) corresponding to the conjugated diene compound-nonconjugated olefin copolymer (A). It was. The yield of the obtained copolymer BBR was about 65% by mass, the diene content was 55 mol%, and the weight average molecular weight (Mw) was 300,000.

(Examples 1-8 and Comparative Examples 1-6)
As samples of the rubber compositions of Examples 1 to 8 and Comparative Examples 1 to 6, rubber compositions were prepared according to the formulation shown in Tables 1 and 2.
Then, after using the rubber composition of each sample to prepare a master batch by adding compounds according to the master batch column shown in Table 3, the final batch by adding compounds according to the final batch column shown in Table 3 Then, the adjusted final batch was vulcanized at 160 ° C. for 20 minutes to prepare a vulcanized rubber sample. In addition, “phr” described in Tables 1 and 2 is a ratio with respect to 100 parts by mass of the rubber component.

なお、比較例４では、ジシクロペンタジエン樹脂の含有量が少ないことで、作業性が低下する。比較例５では、ジシクロペンタジエン樹脂の含有量が多いことで、作業性及び力学特性が低下する。また、作業性とは、加工性が良いことを示す。

In Comparative Example 4, workability is reduced due to the low content of dicyclopentadiene resin. In Comparative Example 5, the workability and the mechanical properties are reduced due to the large content of the dicyclopentadiene resin. Moreover, workability | operativity shows that workability is good.

Brands such as polymers used in the compositions of Tables 1 to 3 are described below.
EPDM ^{* 1} : Non-conjugated diene compound-EPDM as a non-conjugated olefin: manufactured by JSR, EP 96 (diene content: 5.8 wt%)
NR ^{* 2} : natural rubber as a conjugated diene polymer Grade RSS # 4
Carbon Black: ISAF grade, Tokai Carbon Seast 6
Fatty acid: Stearic acid Anti-aging agent 1: “NOCRACK (registered trademark) 224” (trade name), manufactured by Ouchi Shinsei Chemical Co., Ltd. (2,2,4-trimethyl-1,2-dihydroquinoline polymer)
Anti-aging agent 2: “KUMANOX 13” (trade name), KUMHO. INC, N- (1,3-dimethylbutyl) N′-phenyl-p-phenylenediamine dicyclopentadiene resin 1: QUINTON 1920, manufactured by Nippon Zeon
Dicyclopentadiene resin 2: Marukaretsu M-890A manufactured by Maruzen Petrochemical Co., Ltd.
Softener: Aromatically modified terpene hydrocarbon resin: YS resin TO105 (trade name), Yashara Chemical-made anti-aging agent 3: Ouchi Shinsei Chemical Industry Noxeller CZ-G, N-cyclohexyl-2-benzothiazolylsulfenamide retarder : Toray Fine Chemicals Retarder CTP, PVI (N- (cyclohexylthio) -phthalimide)

  As is clear from Tables 1 to 3, the rubber compositions of Examples 1 to 8 are conjugated diene polymer (A), conjugated diene compound-nonconjugated olefin copolymer (B), and ethylene-propylene-diene rubber. A rubber composition for covering a rubber bearing, comprising a rubber component containing a non-conjugated diene compound-non-conjugated olefin copolymer (C) containing a resin (D), and 100 parts by weight of the rubber component, By including 5 parts by mass to 60 parts by mass of the resin, compared to Comparative Examples 1 to 6, the crack growth property, weather resistance (ozone resistance), and fracture resistance of the rubber for covering a rubber support are improved. In addition, it was possible to achieve sufficient attenuation.

  The rubber composition for covering a rubber support of the present invention is suitably used for producing a rubber for covering a rubber support. The rubber for covering a rubber support can be used for a covering layer of a rubber support.

4 Mounting face plate 5 Mounting face plate 11 Soft plate 12 Hard plate 13 Rubber laminate 14 Cover layer 20 Rubber bearing

Claims (7)

Rubber containing a conjugated diene polymer (A), a conjugated diene compound-nonconjugated olefin copolymer (B), and a nonconjugated diene compound-nonconjugated olefin copolymer (C) containing ethylene-propylene-diene rubber A rubber composition for covering a rubber bearing, comprising a component and a resin (D),
Including 5 to 60 parts by mass of the resin (D) with respect to 100 parts by mass of the rubber component ;
A rubber composition for covering a rubber bearing, wherein the conjugated diene compound-nonconjugated olefin copolymer (B) is a propylene-butadiene copolymer .   2. The rubber composition for covering a rubber bearing according to claim 1, wherein a ratio of the non-conjugated olefin-derived portion in the copolymer (B) is 60 mol% or less.   The rubber for covering a rubber bearing according to claim 1 or 2, wherein the content of ethylene-propylene-diene rubber in the non-conjugated diene compound-non-conjugated olefin copolymer (C) is 10% by mass or more. Composition.   The rubber composition for covering a rubber bearing according to any one of claims 1 to 3, wherein the copolymer (B) has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.   5. The rubber composition for covering a rubber bearing according to claim 1, wherein the copolymer (B) has a molecular weight distribution (Mw / Mn) of 10 or less. The resin (D) is a polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, aliphatic / alicyclic C5 petroleum resin, C5 / C9 petroleum resin, C9 petroleum resin, terpene resin, The rubber composition for covering a rubber bearing according to any one of claims 1 to 5 , which is at least one selected from the group consisting of these copolymers and modified products. A rubber for covering a rubber bearing, wherein the rubber composition for covering a rubber bearing according to any one of claims 1 to 6 is used.

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