JP5798941B2 - Rubber composition and pneumatic tire - Google Patents

Description

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

  In general, the crown part of the tire skin is protected by a protective member such as a particularly thick tread rubber or belt, but such a protective member is not provided on the side wall part, so that it is subject to cut damage from the outside. It is known that this can lead to air leaks. Thus, various attempts have been made in the past as measures for preventing such cut damage and the resulting air leakage, but there is still room for improvement.

  For example, as a first type of the above-described trial, there is known a method of reducing the depth of cut scratches in the sidewall portion by providing a reinforcing cord layer made of a fiber material outside the carcass layer in the sidewall portion of the tire. (Japanese Patent Laid-Open No. 47-651). However, although this method can increase the effect to some extent on the cut flaw itself, once the cut flaw occurs, it cannot stop the progress of the flaw, and the reinforcing cord layer There is a problem that separation tends to occur from the end.

  Further, as a second type of the above-described trial, a technique is known in which a thick rubber layer is disposed inside the carcass layer in the sidewall portion of the tire (Japanese Patent Publication No. 45-40383). However, the rubber layer is expected to prolong the time until air leakage when cut flaws are received, but it cannot fundamentally stop the progress of flaw growth, and is resistant to air leakage. It cannot contribute sufficiently to the improvement. Moreover, when the rubber layer is thickened in this way, the heat generation of the tire increases due to an increase in the amount of rubber, and the distortion of the bead portion and the belt layer end increases, resulting in a decrease in tire durability. However, it is difficult to manufacture, and there are disadvantages such as an increase in cost.

  Furthermore, in recent years, attempts have been made to reduce the thickness of the side rubber itself for the purpose of weight reduction in order to achieve the fuel saving of the tire, and further improvement of the cut resistance of the sidewall portion has become an issue. Yes.

JP 47-651 A Japanese Examined Patent Publication No. 45-40383

  Therefore, an object of the present invention is to provide a rubber composition that solves the above-mentioned problems of the prior art and is excellent in cut resistance and crack growth resistance. Another object of the present invention is to provide a pneumatic tire which is excellent in cut resistance and crack growth resistance of a sidewall portion and whose air leakage resistance is remarkably improved.

  As a result of intensive studies to achieve the above object, the present inventor has formulated a specific inorganic compound powder while using a copolymer of a conjugated diene and a non-conjugated olefin as at least a part of the rubber component. Thus, the resulting rubber composition has excellent cut resistance and crack growth resistance, and the use of such a rubber composition for a tire sidewall makes it possible to reduce the cut resistance and crack growth resistance of the sidewall. As a result, it was found that the air leakage resistance performance of the tire was remarkably improved, and the present invention was completed.

That is, the rubber composition of the present invention has the following general formula (I) with respect to 100 parts by mass of a rubber component containing 1 to 100% by mass of a conjugated diene-nonconjugated olefin copolymer:
nM · xNa ₂ O · ySiO ₂ · zH ₂ O (I)
[Wherein, M is an oxide or hydroxide of at least one metal selected from Al, Mg, Ti, and Ca, n is an integer of 0 to 5, and x is 0 to 1.0. , Y is an integer of 0-30, z is an integer of 0-10, provided that at least one of n, x and y is not 0], and has a diameter of 10 μm or less. The inorganic compound powder is blended in an amount of 2 to 30 parts by mass. Such a rubber composition of the present invention is excellent in cut resistance and crack growth resistance.

  In a preferred example of the rubber composition of the present invention, the inorganic compound powder is silica, aluminum silicate, aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, titanium white, titanium black, talc, attapulgite, clay, Selected from the group consisting of kaolin, pyrophyllite, and bentonite. In this case, the cut resistance of the rubber composition can be further improved.

  Moreover, the pneumatic tire of the present invention is characterized in that the above rubber composition is applied to a side rubber of a sidewall portion. In the pneumatic tire of the present invention, after the cut flaw is received, the progress of the cut flaw on the inner surface of the tire is suppressed, and the air leakage resistance performance is remarkably improved.

  In a preferred example of the pneumatic tire of the present invention, the thickness of the side rubber at the position having the maximum tire width is smaller than the sum of the thicknesses of the inner liner and the carcass ply at the same position. In this case, compared with the case where the conventional rubber composition is used, the improvement range of the air leakage resistance performance is large, and the effect of the present invention becomes more remarkable.

  According to the present invention, a rubber composition excellent in cut resistance and crack growth resistance, in which a specific inorganic compound powder is blended using a conjugated diene-nonconjugated olefin copolymer as at least a part of a rubber component. Can be provided. Further, according to the present invention, the rubber composition is used for a sidewall, and provides a pneumatic tire having excellent cut resistance and crack growth resistance of the sidewall portion, and air leakage performance is greatly improved. can do.

  Hereinafter, the present invention will be described in detail by illustrating its embodiments. The rubber composition of the present invention is represented by the general formula (I) with respect to 100 parts by mass of a rubber component containing 1 to 100% by mass of a conjugated diene-nonconjugated olefin copolymer. It is characterized by blending 2 to 30 parts by mass of one kind of inorganic compound powder.

  When a hard protrusion pierces a rubber member using the rubber composition of the present invention, the tip of the protrusion hits the inorganic compound powder in the rubber member. At this time, the input energy from the tip of the protrusion is received by the entire inorganic compound powder, so that the energy is dissipated and the energy input to the rubber member is reduced. As a result, even when the same energy is input from the tip of the protrusion, it is considered that the rubber member using the rubber composition of the present invention in which the inorganic compound powder is blended is difficult to cut and the cut resistance is improved. However, the rubber composition containing the inorganic compound powder is inferior in crack growth resistance. Therefore, in the present invention, by using a combination of an inorganic compound powder and a conjugated diene-nonconjugated olefin copolymer excellent in crack growth resistance, the crack growth resistance and cut resistance of the rubber composition can be improved. Highly compatible.

  The rubber component of the rubber composition of the present invention contains a conjugated diene-nonconjugated olefin copolymer. By using a conjugated diene-nonconjugated olefin copolymer as the rubber component of the rubber composition, the crack growth resistance of the rubber composition can be improved.

  Content in the rubber component of the said conjugated diene non-conjugated olefin copolymer is the range of 1-100 mass%, and the range of 10-90 mass% is preferable. When the content of the conjugated diene-nonconjugated olefin copolymer in the rubber component is less than 1% by mass, the effect of improving the crack growth resistance of the rubber composition cannot be sufficiently obtained.

  The conjugated diene-nonconjugated olefin copolymer is a copolymer of a conjugated diene and a nonconjugated olefin, and includes a conjugated diene and a nonconjugated olefin as monomer unit components in the copolymer. The content of the conjugated diene-derived moiety in the conjugated diene-nonconjugated olefin copolymer is preferably 40 mol% or more, more preferably 60 mol% or more. On the other hand, the content of the non-conjugated olefin-derived portion in the conjugated diene-nonconjugated olefin copolymer is preferably 60 mol% or less, and more preferably 40 mol% or less. If the content of the non-conjugated olefin-derived portion in the conjugated diene-nonconjugated olefin copolymer is 60 mol% or less, the kneadability and workability with the inorganic compound powder are good, and the crack growth resistance is sufficiently improved. be able to.

  Further, the cis-1,4 bond content of the conjugated diene-derived portion in the conjugated diene-nonconjugated olefin copolymer is preferably 50% or more, particularly preferably more than 92%, and most preferably 95% or more. If the cis 1,4-bond amount of the conjugated diene-derived moiety is 50% or more, the crack growth resistance can be sufficiently improved. Further, by making the amount of cis 1,4-bond of the conjugated diene-derived portion more than 92%, the crack growth resistance can be further improved, and the amount of cis 1,4-bond of the conjugated diene-derived portion is 95%. By setting it as the above, it becomes possible to improve crack growth resistance further. The cis-1,4 bond amount is an amount in the conjugated diene-derived portion and is not a ratio to the entire copolymer.

  In the conjugated diene-nonconjugated olefin copolymer, the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene, and has excellent heat resistance and a double bond in the main chain of the copolymer. It is possible to increase the degree of design freedom as an elastomer by controlling the crystallinity. The non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin preferably has 2 to 10 carbon atoms. 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. Here, the non-conjugated olefin does not include styrene. Since the α-olefin has a double bond at the α-position of the olefin, it can be efficiently copolymerized with a conjugated diene. 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 non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  On the other hand, in the conjugated diene-nonconjugated olefin copolymer, the conjugated diene used as a monomer preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated dienes may be used alone or in combination of two or more. Using any of the specific examples of the conjugated diene described above, the desired copolymer can be prepared by the same mechanism.

  The conjugated diene-nonconjugated olefin copolymer preferably has a polystyrene equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000 from the viewpoint of application to a polymer structure material. More preferably, it is -1,000,000, and it is especially preferable that it is 50,000-600,000. If the Mw exceeds 10,000,000, the moldability may be deteriorated. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. If the molecular weight distribution exceeds 10, the physical properties may not be uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The content of 1,2 adducts (including 3,4 adducts) of the conjugated diene in the conjugated diene-derived part of the conjugated diene-nonconjugated olefin copolymer is preferably 5% or less, more preferably 3% or less. 2.5% or less is particularly preferable. When the content of 1,2 adducts (including 3,4 adducts) of conjugated dienes in the conjugated diene-derived part of the conjugated diene-nonconjugated olefin copolymer is 5% or less, crack-resistant growth of the copolymer When it is 2.5% or less, the crack growth 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 conjugated diene-derived portion and is not a ratio to the whole copolymer. Moreover, the 1,2-adduct part content (including 3,4-adduct part) content of the conjugated diene in the conjugated diene-derived part has the same meaning as the 1,2-vinyl bond amount when the conjugated diene is butadiene.

  Examples of the chain structure of the conjugated diene-nonconjugated olefin copolymer include a block copolymer, a random copolymer, a tapered copolymer, and an alternating copolymer.

The block copolymer has a structure of (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of monomer units of non-conjugated olefins). And B is a block part composed of monomer units of conjugated dienes, 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-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

  When the conjugated diene-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, so that the copolymer does not undergo phase separation and the block portion. The crystallization temperature derived from 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.

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

  The alternating copolymer is a polymer having a structure in which conjugated dienes and nonconjugated olefins are alternately arranged (a molecular chain structure of -ABABABAB- when A is a nonconjugated olefin and B is a conjugated diene). is there.

  Next, the manufacturing method which can manufacture the said conjugated diene-nonconjugated olefin copolymer is demonstrated in detail. However, the production method described in detail below is merely an example, and the copolymer according to the present invention is obtained by polymerizing a conjugated diene and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition. It is done.

  In the method for producing the conjugated diene-nonconjugated olefin copolymer, the polymerization by the usual coordination ion polymerization catalyst is used except that the polymerization catalyst described later or the first, second and third polymerization catalyst compositions are used. In the same manner as in the method for producing a coalescence, a monomeric conjugated diene and a non-conjugated olefin can be copolymerized.

  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.

  In the method for producing the conjugated diene-nonconjugated olefin copolymer, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system containing a conjugated diene and a nonconjugated olefin as monomers. 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 a conjugated diene and a nonconjugated olefin.

  Moreover, in the manufacturing method of the said conjugated diene-nonconjugated olefin copolymer, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  The polymerization reaction of the conjugated diene 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 and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

  In the method for producing a copolymer, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa when the conjugated diene and the non-conjugated olefin are polymerized. 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 a copolymer, when polymerizing a conjugated diene and a non-conjugated olefin, the concentration (mol / l) of the conjugated diene at the start of polymerization and the concentration (mol / l) of the non-conjugated olefin are as follows: formula:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.0
It is preferable to satisfy the relationship. By setting the non-conjugated olefin concentration / conjugated diene concentration value to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Also, the following formula:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.3
More preferably, the following relationship is satisfied:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.7
It is even more preferable to satisfy this relationship.

（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（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、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（IV）：

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

(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 (III):

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

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

  The first polymerization catalyst composition may further contain other components 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 formula (II) and formula (III), 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. Incidentally, the two Cp ^R in the general formula (II) and formula (III) may each be the same 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）のものが例示される。一般式（IV）において、上記インデニル環を基本骨格とするＣｐ^R'は、一般式（II）のＣｐ^Rと同様に定義され、好ましい例も同様である。一般式（IV）において、上記フルオレニル環を基本骨格とするＣｐ^R'は、Ｃ₁₃Ｈ_9-XＲ_X又はＣ₁₃Ｈ_17-XＲ_Xで示され得る。ここで、Ｘは０〜９又は０〜１７の整数である。また、Ｒはそれぞれ独立してヒドロカルビル基又はメタロイド基であることが好ましい。ヒドロカルビル基の炭素数は１〜２０であることが好ましく、１〜１０であることが更に好ましく、１〜８であることが一層好ましい。該ヒドロカルビル基として、具体的には、メチル基、エチル基、フェニル基、ベンジル基等が好適に挙げられる。一方、メタロイド基のメタロイドの例としては、ゲルミルＧｅ、スタニルＳｎ、シリルＳｉが挙げられ、また、メタロイド基はヒドロカルビル基を有することが好ましく、メタロイド基が有するヒドロカルビル基は上記のヒドロカルビル基と同様である。該メタロイド基として、具体的には、トリメチルシリル基等が挙げられる。 In the half metallocene cation complex represented by the general formula (IV), 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. As Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton, specifically, the following:

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

The metallocene complex represented by the general formula (III) 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 (IV) described below, and preferred groups are also the same.

  In the general formula (IV), 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 (IV), 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. Of these, 2,4,6-triisopropylthiophenoxy group is preferred. Arbitrariness. In the general formula (IV), 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 (IV), 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 (IV), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable. In the general formula (IV), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In formula (IV), [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 formula (II) and the formula (III) and the half metallocene cation complex represented by the general formula (IV) 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. In addition, the metallocene complex represented by the general formula (II) and the formula (III) and the half metallocene cation complex represented by the general formula (IV) may be present as a monomer. It may exist as a body or higher multimer.

（式中、Ｘ''はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and 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 example of reaction for obtaining the metallocene complex represented by general formula (II) 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 (III) 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 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. The reaction example for obtaining the metallocene complex represented by the general formula (III) is shown below.

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

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

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

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. 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 (IV) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (IV) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (V) 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 (IV You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (II) or the formula (III) and an ionic compound represented by the general formula [A] ⁺ [B] ^- A half metallocene cation complex represented by the formula (IV) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (II) and (III) and the half metallocene cation complex represented by the general formula (IV) 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.

  Furthermore, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (II) and the formula (III) and the half metallocene cation complex represented by the above general formula (IV), respectively, By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

Next, the second polymerization catalyst composition used in the method for producing a conjugated diene-nonconjugated olefin copolymer according to the present invention will be described. As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can be preferably mentioned.

Further, when the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (VI):
YR ¹ _a R ² _b R ³ _c (VI)
[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]. Including.

  Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. The second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition. In the polymerization reaction system, the concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

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

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (VII) or (VIII):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (VII)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (VIII)
[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 name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component. As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable. The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred. Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred. The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced. Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is an organometallic compound represented by the above general formula (VI), and the following general formula (VI-a):
AlR ¹ R ² R ³ ... (VI-a)
[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 formula (VI-a) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentyl. Aluminum, 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, dihydrogen hydride Isohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Examples thereof include dihydride and isobutylaluminum dihydride. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

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

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^A and R ^B each independently represents a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by By using the metallocene composite catalyst, a conjugated diene-nonconjugated olefin copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (IX) 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 (IX), 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 (IX), 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 (IX), 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 (IX), 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 (X), 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 (X), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^R 's in formula (X) may be the same as or different from each other. In the formula (X), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R ^B is coordinated μ to M ¹及A ^l . Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure. In the above formula (X), 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, represented by the following formula (XI):

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

  Further, the third polymerization catalyst composition is characterized in that it contains the metallocene composite catalyst and a boron anion, and further, other components contained in the polymerization catalyst composition containing a normal metallocene catalyst, For example, it preferably contains a cocatalyst and the like. 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. It becomes possible.

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

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

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

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

  Further, even if the polymerization catalyst composition is not used, that is, even when a normal coordination ion polymerization catalyst is used, by adjusting how the monomer is charged into the polymerization reaction system, The copolymer can be produced. That is, the second method for producing the copolymer is characterized in that the chain structure of the copolymer is controlled by controlling the input of the conjugated diene in the presence of the non-conjugated olefin, thereby providing a copolymer. The arrangement of monomer units in the polymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example. Here, the conjugated diene charging method may be either continuous charging or split charging, and may be a combination of continuous charging and split charging. Moreover, continuous injection means adding for a fixed time at a fixed addition rate, for example. Specifically, it is possible to control the concentration ratio of the monomers in the polymerization reaction system by dividing or continuously charging the conjugated diene into the polymerization reaction system for polymerizing the conjugated diene 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 is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the production of the conjugated diene homopolymer. The addition of the conjugated diene may be performed after the polymerization of the nonconjugated olefin is started.

  The rubber component of the rubber composition of the present invention may contain natural rubber (NR) and other synthetic rubbers in addition to the conjugated diene-nonconjugated olefin copolymer described above. Here, examples of the synthetic rubber include synthetic diene rubbers such as synthetic polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butyl rubber (IIR), and halogenated butyl rubber. . These rubber components may be used alone or in combination of two or more.

  The rubber composition of the present invention comprises an inorganic compound powder represented by the above general formula (I) and having a diameter of 10 μm or less. By blending the inorganic compound powder according to the rubber composition, the cut resistance of the rubber composition can be improved.

The inorganic compound powder used in the rubber composition of the present invention is at least one kind represented by the above general formula (I). In the above general formula (I), M is selected from Al, Mg, Ti, and Ca. It is an oxide or hydroxide of at least one metal, n is an integer of 0 to 5, x is 0 to 1.0, y is an integer of 0 to 30, and z is 0 to 10 Provided that at least one of n, x and y is not 0. Examples of the inorganic compound powder represented by the general formula (I) include silica (for example, SiO ₂ ), aluminum silicate (for example, Na ₂ O.30SiO ₂ .2Al ₂ O ₃ .10H ₂ O), hydroxide Aluminum (eg, Al (OH) ₃ ), alumina (eg, Al ₂ O ₃ ), magnesium hydroxide (eg, Mg (OH) ₂ ), magnesium oxide (eg, MgO ₂ ), titanium white (eg, TiO ₂₎ ), titanium black (e.g., TiO _2n-1), talc _{(e.g., 3MgO · 4SiO 2 · H 2} O), attapulgite _{(e.g., 5MgO · 8SiO 2 · 9H 2} O), clays (e.g., Al ₂ O ₃ · 2SiO ₂ ), kaolin (eg, Al ₂ O ₃ .2SiO ₂ .2H ₂ O), pyrophyllite (eg, Al ₂ O ₃ .4SiO ₂ .H ₂ O), bentonite (eg, Al ₂ O _3. 4SiO ₂ .2H ₂ O) and the like are preferable. These inorganic compound powders may be used alone or in a combination of two or more.

  The inorganic compound powder has a diameter of 10 μm or less, preferably 8 μm or less. If the diameter of the inorganic compound powder exceeds 10 μm, the inorganic compound powder becomes a fracture nucleus, and the effect of improving the cut resistance of the rubber composition cannot be sufficiently obtained. In the present invention, the diameter of the inorganic compound powder is a volume average particle diameter measured by a laser light scattering method. Here, a laser light scattering type particle size distribution measuring device (Horiba, Ltd., LA910) was used, and the sample was added to water as a dispersion while stirring until an appropriate amount was obtained, and after ultrasonic dispersion for 1 minute, measurement was performed. . The relative refractive index used was 1.10.

  The compounding quantity of the said inorganic compound powder is the range of 2-30 mass parts with respect to 100 mass parts of said rubber components, and the range of 5-15 mass parts is preferable. When the blending amount of the inorganic compound powder is less than 2 parts by mass with respect to 100 parts by mass of the rubber component, the effect of improving the cut resistance of the rubber composition cannot be sufficiently obtained. The crack growth resistance of the composition deteriorates.

  In addition to the rubber component and inorganic compound powder described above, the rubber composition of the present invention further includes a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a scorch preventing agent, zinc white, stearic acid, and silane coupling. A compounding agent usually used in the rubber industry such as an agent can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used. The rubber composition for tires of the present invention is prepared by kneading the rubber component containing at least a conjugated diene-nonconjugated olefin copolymer with the inorganic compound powder and various compounding agents appropriately selected as necessary. It can be produced by extrusion or the like. In addition, the rubber composition of this invention can be used for various rubber articles, such as a pneumatic tire mentioned later, a hose, a belt.

  The pneumatic tire according to the present invention is characterized in that the tire rubber composition is applied to a side rubber of a sidewall portion. Here, it is preferable that the thickness of the side rubber at the position having the maximum tire width is smaller than the sum of the thicknesses of the inner liner and the carcass ply at the same position. In this case, compared with the pneumatic tire using the conventional rubber composition, the improvement range of the air leakage resistance performance is large, and the effect of the present invention becomes more remarkable. In addition, as gas with which the pneumatic tire of this invention is filled, the inert gas, such as the air which changed normal or oxygen partial pressure, or nitrogen, is mentioned.

  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.

<Synthesis of ethylene-butadiene copolymer rubber (EBR)>
After adding 160 mL of toluene solution to a sufficiently dry 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. And 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 mL of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass 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 an ethylene-butadiene copolymer (EBR). The yield of EBR obtained was 12.50 g.

  About obtained EBR, ethylene content rate, a weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured with the following method. As a result, as the microstructure of the butadiene portion in the obtained EBR, the cis-1,4 bond content was 98%, and the 1,2-vinyl bond content was 1.2%. The weight average molecular weight Mw was 350,000, and the molecular weight distribution Mw / Mn was 2.2. The ethylene content was 7 mol% (butadiene content was 93 mol%). Furthermore, the block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block.

(Copolymer microstructure (1,2-vinyl bond content, cis-1,4 bond content))
The microstructure (1,2-vinyl bond amount) of the butadiene moiety in the copolymer was determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm) according to the 1,2-vinyl bond component (5.0 -5.1 ppm) and the integral ratio of the entire butadiene bond component (5-5.6 ppm). Further, the microstructure (cis-1,4 bond amount) of the butadiene moiety in the copolymer is determined based on the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). (26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm) were obtained from the integral ratio.

(Content of ethylene-derived part of EBR)
The content (mol%) of the ethylene-derived portion in the obtained EBR was determined based on the total ethylene bond component (28.5-30.0 ppm) according to ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). ) And the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm).

(Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of EBR)
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.

(Block polyethylene melting temperature of copolymer (DSC peak temperature))
Differential scanning calorimetry (DSC) was performed in accordance with JIS K7121-1987, a DSC curve was drawn, and a block polyethylene melting temperature (DSC peak temperature) was measured. In order to avoid the influence of impurities such as single polymer and catalyst residue, the measurement was performed by immersing the copolymer in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then using the dried rubber component as a sample. did.

<Preparation of rubber composition and production of tire>
A rubber composition blended according to the blending table shown in Table 1 was prepared, and the rubber composition was disposed as a side rubber on a sidewall portion of the tire to produce a tire having a size of 175 / 70R14. The crack growth resistance was measured by the following method.

* 1 Polybutadiene rubber, 150L made by Ube Industries
* 2 Ethylene-butadiene copolymer rubber (EBR) synthesized by the above method
* 3 Seest F, manufactured by Tokai Carbon Co., Ltd. * 4 Details are shown in Table 2 to Table 4. * 5 Microcrystalline wax, Ozoace 0701, manufactured by Nippon Seiwa Co., Ltd. * 6 Nocrack 6C, manufactured by Ouchi Shinsei Chemical Co., Ltd. * 7 Noxeller D, manufactured by Ouchi Shinsei Chemical Co., Ltd. * 8 Noxeller DM, manufactured by Ouchi Shinsei Chemical Co., Ltd. * 9 Sunseller CM-G, manufactured by Sanshin Chemical Industry Co., Ltd.

<Cut resistance test (actual vehicle)>
The test tire is assembled to the rim of size 14-5.5J on the left rear wheel of a 2 liter passenger car, the internal pressure is 150 kPa, the load mass is the driver + 60 kg, and the speed is changed from 50 to 80 km / h. The rate at which cuts occurred when the 60 mm protrusions installed on the vehicle were overcome was evaluated as an index. The index values in Table 2 were obtained using the tire values of Comparative Example 1 as controls, and the index values in Table 3 were obtained using the tire values of Comparative Example 5 as controls. The index value in the figure was obtained by using the value of the tire of Comparative Example 8 as a control, and the larger the value, the better the cut resistance performance.

<Crack growth resistance test (constant stress)>
A tensile test according to JIS K6251 was performed on the JIS No. 3 test piece, and a tensile stress at 100% elongation (Md 100%) was obtained. Next, a 0.5 mm crack was made in the center of the JIS No. 3 test piece, repeated fatigue was given at a constant stress of Md 100% at room temperature, and the number of times until the test piece was broken was measured. In Table 2, the number of times until the test piece of Comparative Example 1 is ruptured is shown as an index in 100, and in Table 3, the number of times until the test piece of Comparative Example 5 is ruptured is shown as an index, 100. In Table 4, the number of times until the test piece of Comparative Example 8 was broken was represented by 100 as an index. The larger the index value, the greater the number of times until the test piece reaches breakage, indicating better crack growth resistance.

  From the results shown in Tables 2 to 4, by adding an inorganic compound powder, the crack growth resistance of the rubber composition is reduced, but a conjugated diene-nonconjugated olefin copolymer such as EBR is used as the rubber component. By using the rubber composition containing the inorganic compound powder and the conjugated diene-nonconjugated olefin copolymer for the sidewall portion of the tire, the decrease in crack growth resistance of the rubber composition can be suppressed. It can be seen that the cut resistance of the tire can be improved.

Claims (4)

With respect to 100 parts by mass of a rubber component containing 1 to 100% by mass of a conjugated diene-nonconjugated olefin copolymer, the following general formula (I):
nM · xNa ₂ O · ySiO ₂ · zH ₂ O (I)
[Wherein, M is an oxide or hydroxide of at least one metal selected from Al, Mg, Ti, and Ca, n is an integer of 0 to 5, and x is 0 to 1.0. , Y is an integer of 0-30, z is an integer of 0-10, provided that at least one of n, x and y is not 0], and has a diameter of 10 μm or less. A rubber composition comprising 2 to 30 parts by mass of the inorganic compound powder.   The inorganic compound powder is selected from the group consisting of silica, aluminum silicate, aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, titanium white, titanium black, talc, attapulgite, clay, kaolin, pyrophyllite, and bentonite. The rubber composition according to claim 1, wherein the rubber composition is selected.   The pneumatic tire which applied the rubber composition of Claim 1 or 2 to the side rubber of a side wall part.   The pneumatic tire according to claim 3, wherein the thickness of the side rubber at the position having the maximum tire width is smaller than the sum of the thicknesses of the inner liner and the carcass ply at the same position.