JP2016128552A - Rubber composition and tire using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition improving ozone resistance and crack growth resistance, and a tire improved in ozone resistance and crack growth resistance.SOLUTION: The rubber composition contains a polymer component comprising a conjugated diene compound-nonconjugated olefin copolymer and a nonconjugated olefin polymer, and a binder. The nonconjugated olefin polymer is contained in an amount of 10 mass% or more based on the polymer component. The tire includes a member having the rubber composition.SELECTED DRAWING: None

Description

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

Conventionally, various attempts have been made to improve the weather resistance of rubber products such as tires. For example, in Patent Document 1, as a method for improving weather resistance, a) a linear, branched or cyclic hydrocarbon compound having 18 to 55 carbon atoms is used for 100 parts by mass of rubber having an unsaturated bond. And b) a polyethylene oxide-polypropylene oxide copolymer having an average molecular weight of 1500 to 8000 and an ethylene oxide / propylene oxide ratio of 10/90 to 80/20. It has been proposed to use a rubber composition characterized by blending 5.0 parts by mass.
In addition, in order to reduce the viscosity at the time of unvulcanized and to improve processability, Patent Document 2 discloses a rubber containing at least one of a diene synthetic rubber and a natural rubber and a conjugated diene compound-nonconjugated olefin copolymer. A rubber composition for a tire containing a component, wherein a terpene phenol resin, a C5 petroleum resin, a C9 petroleum resin, a C5 / C9 copolymer resin, a dicyclopentadiene (DCPD) resin, an alkylphenol is used as a heat softening resin There has been proposed a rubber composition for tires comprising at least one selected from the group consisting of an acetylene resin and a p-tert-butylphenol-acetylene resin.

JP 2007-186565 A JP 2013-185048 A

However, there is still a demand for improving the weather resistance of rubber products such as tires.
In order to improve the weather resistance of rubber products such as tires, the present inventors have focused on the importance of improving the ozone resistance and crack growth resistance of rubber compositions.
The present invention has been made from this point of view, and it is an object of the present invention to provide a rubber composition for improving ozone resistance and crack growth resistance and a tire having improved ozone resistance and crack growth resistance. It is.

  As a result of intensive studies to solve the above problems, the present inventor added a binder to a polymer component having a conjugated diene compound-nonconjugated olefin copolymer and a nonconjugated olefin polymer, and It has been found that a rubber composition capable of solving the problem can be obtained by adding a specific amount of the conjugated olefin polymer to the polymer component. The present invention has been completed based on such findings.

That is, the present invention
[1] A rubber composition comprising a polymer component having a conjugated diene compound-nonconjugated olefin copolymer and a nonconjugated olefin polymer, and a binder, wherein the nonconjugated olefin polymer is based on the polymer component. A rubber composition containing 10% by mass or more,
[2] The rubber composition according to [1], wherein the binder is a free radical generator,
[3] The rubber composition according to the above [2], wherein the free radical generator is at least one selected from peroxides and azo polymerization initiators.
[4] The conjugated diene compound in the conjugated diene compound-nonconjugated olefin copolymer is a diene rubber containing at least one of polybutadiene and polyisoprene, according to any one of the above [1] to [3]. Rubber composition.
[5] The rubber composition according to any one of [1] to [4], wherein the non-conjugated olefin polymer is an olefin polymer containing at least one selected from polyethylene, polypropylene, and polybutene, and ,
[6] A tire including a member having the rubber composition according to any one of [1] to [5] is provided.

  According to the present invention, it is possible to provide a rubber composition that improves ozone resistance and crack growth resistance, and a tire that has improved ozone resistance and crack growth resistance.

First, the rubber composition of the present invention will be described.
[Rubber composition]
The rubber composition of the present invention comprises a conjugated diene compound-nonconjugated olefin copolymer, a nonconjugated olefin polymer, and a binder, and the nonconjugated olefin polymer is 10% by mass or more based on the polymer component. It is contained.
Furthermore, the rubber composition of the present invention is a rubber composition comprising a polymer component having a conjugated diene compound-nonconjugated olefin copolymer and a nonconjugated olefin polymer, and a binder, from the viewpoint of ozone resistance. The non-conjugated olefin polymer is preferably 20% by mass or more, more preferably 30% by mass with respect to the polymer component.

<Conjugated diene compound-nonconjugated olefin copolymer>
There is no restriction | limiting in particular as content in the rubber component of the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, From a viewpoint of a balance with crack growth resistance, a polymer More than 30% by mass, preferably 50% by mass or more, and less than 100% by mass, more preferably 90% by mass or less, based on the total amount of components.
When the content of the conjugated diene compound-nonconjugated olefin copolymer in the rubber component is less than 10% by mass, the effect of improving crack growth resistance, heat resistance, and ozone resistance is small or improved. It may not be effective.

  In the conjugated diene compound-nonconjugated olefin copolymer, the conjugated diene compound-derived portion (conjugated diene portion) is polybutadiene, synthetic polyisoprene, natural rubber, styrene-butadiene-random copolymer, styrene-isoprene-random copolymer. It is preferably one or more polymers selected from ethylene-butadiene copolymers and propylene-butadiene copolymers, and one kind selected from polybutadiene, synthetic polyisoprene, natural rubber, and ethylene-butadiene copolymers. The above polymer is particularly preferable, and an ethylene-butadiene copolymer (EBR) is more preferable. Examples of the ethylene-butadiene copolymer include a multiblock copolymer, an alternating copolymer, and a random copolymer, and a multiblock copolymer is particularly desirable.

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

As content of the nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, 50 mol% or less is preferable and it is preferable that it is 30 mol%-10 mol%.
When the content of the non-conjugated olefin-derived portion exceeds 50 mol%, kneadability and workability with the filler may become a problem.

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

The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.
The conjugated diene compound-nonconjugated olefin copolymer can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

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

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

The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene compound-nonconjugated olefin copolymer is preferably 10 or less, more preferably 6 or less. preferable. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform.
Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

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

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

[First polymerization catalyst composition]
The polymerization catalyst composition includes the following general formula (I):

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

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

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

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

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

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

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

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

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

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

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

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

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Further, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining, the molecular weight of the cis-1,4 bond amount and the resulting conjugated diene compound-nonconjugated olefin copolymer can be increased.

[Second polymerization catalyst composition]
In addition, as the polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds (hereinafter also referred to as a second polymerization catalyst composition) can be preferably exemplified.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is characterized by including.

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

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

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

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

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

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

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

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

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

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

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

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

The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
Examples of the organic compound containing the active halogen include benzyl chloride.

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

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

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

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

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

[Metalocene-based composite catalyst]
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.] By using the metallocene polymerization catalyst, a conjugated diene compound-nonconjugated olefin copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

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

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

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

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

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

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

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

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

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

The metallocene composite catalyst is, for example, in a solvent in the following formula (XVI):

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

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

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

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

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

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

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

[Third polymerization catalyst composition]
The polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, as in the metallocene composite catalyst, since it further contains a boron anion, the content of each monomer component in the conjugated diene compound-nonconjugated olefin copolymer Can be controlled arbitrarily.

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

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

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

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

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

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

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer, the polymerization reaction of the conjugated diene compound and the nonconjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the 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 the conjugated diene compound-nonconjugated olefin copolymer, when the conjugated diene compound is polymerized with a nonconjugated olefin other than the conjugated diene compound, the pressure of the nonconjugated olefin is 0.1 MPa to 10 MPa. It is preferable. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Moreover, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches a peak, and therefore the pressure of the non-conjugated olefin is preferably 10 MPa or less.

In the method for producing the conjugated diene compound-nonconjugated olefin copolymer, when the conjugated diene compound is polymerized with a nonconjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l). ) And the concentration (mol / l) of the non-conjugated olefin are represented by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

<Non-conjugated olefin polymer>
The non-conjugated olefin polymer in the present invention is preferably at least one polymer selected from polyethylene (PE), polypropylene (PP), and polybutene (PB). The polyethylene (PE) is preferably linear low density polyethylene (LLDPE).

<Binder>
In the rubber composition after vulcanization of the present invention, it is preferable that a chemical bond exists at the interface between the conjugated diene compound-nonconjugated olefin copolymer and the nonconjugated olefin polymer. Here, examples of the chemical bond include a covalent bond, a coordination bond, a hydrogen bond, and a van der Waals bond, and a covalent bond with high bond stability is preferable.
Therefore, the binder in the present invention is preferably a free radical generator.
The free radical generator is preferably at least one selected from peroxides and azo polymerization initiators.

[Peroxide]
Examples of the peroxide include inorganic peroxides and organic peroxides. In the case of a rubber composition for tires, organic peroxides are preferable.
As organic peroxide,
Dicumyl peroxide;
α, α ′-(t-butylperoxy) diisopropylbenzene;
t-butyl cumyl peroxide;
2,5-dimethyl-2,5- (t-butylperoxy) hexane;
Dialkyl peroxides such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;
1,1-di (t-butylperoxy) cyclohexane;
1,1-di (t-hexylperoxy) cyclohexane;
N-butyl 4,4-di (t-butylperoxy) valerate;
2,2-di (t-butylperoxy) butane;
4,4-di (t-butylperoxy) valeric acid n-butyl ester;
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane;
Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexane) propane,
2,2,4-trimethylpentyl peroxyneodecanoate;
Α-cumyl peroxyneodecanoate;
T-butyl peroxyneohexanoate;
T-butyl peroxyneopivalate;
T-butyl peroxyacetate; t-butyl peroxylaurate;
T-butyl peroxybenzoate;
T-butyl peroxyphthalate;
Examples include t-butyl peroxyisophthalate; alkyl peresters such as t-hexyl peroxybenzoate.
The amount of these organic peroxides to be used may be appropriately selected depending on the situation, but the polymer component (the total mass of the conjugated diene compound-nonconjugated olefin copolymer and the nonconjugated olefin polymer) is 100 parts by mass. On the other hand, the range of 0.01-1.0 mass part is preferable.

[Azo-based polymerization initiator]
As the azo polymerization initiator, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile (AMBN), 2,2′-azobis-2,4 -Dimethylvaleronitrile (ADVN), 2,2'-azobis-4-azobiscyanovaleric acid (salt) (ACVA) and the like.
The amount of these azo polymerization initiators to be used may be appropriately selected according to the situation, but the polymer component (the total mass of the conjugated diene compound-nonconjugated olefin copolymer and the nonconjugated olefin polymer) 100 parts by mass The range of 0.01 to 1.0 part by mass is preferable.

(Filler)
In the rubber composition of this invention, a filler can be mix | blended as needed.
As the filler, one or more fillers selected from carbon black and silica are preferably used.
There is no restriction | limiting in particular as said carbon black, From what is conventionally used as a filler of rubber | gum, arbitrary things can be selected suitably and can be used. For example, SRF, GPF, FEF, HAF, ISAF, SAF, etc. are used, and particularly FEF, HAF, ISAF, SAF, etc., which are excellent in bending resistance and fracture resistance, are preferably mentioned, and nitrogen adsorption specific surface area N ₂ SA ( JIS K 6217-2:. conforming to 2001) there is preferably 30 to 150 m ² / g, further preferably 35~130m ² / g.
This carbon black may be used individually by 1 type, and may be used in combination of 2 or more type.
On the other hand, examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among these, wet silica is preferable.
The wet silica preferably has a BET specific surface area (measured based on ISO 5794/1) of 40 to 350 m ² / g. Silica having a BET specific surface area within this range has an advantage that both rubber reinforcement and dispersibility in a rubber component can be achieved. From this viewpoint, silica having a BET specific surface area in the range of 80 to 300 m ² / g is more preferable. As such silica, commercially available products such as “Nipsil AQ”, “Nipsil KQ” manufactured by Tosoh Silica Co., Ltd., “Ultrasil VN3” manufactured by Degussa Co., Ltd. can be used.
This silica may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the rubber composition of the present invention, the blending amount of at least one filler selected from carbon black and silica is 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component (total mass of matrix and domain). It is preferably 35 to 100 parts by mass. When the blending amount of the filler is 20 parts by mass or more, the reinforcing effect is exhibited. On the other hand, when it is 120 parts by mass or less, the rolling resistance does not become too large.

(Silane coupling agent)
In the rubber composition of the present invention, when silica is used as a filler, a silane coupling agent can be blended for the purpose of further improving the reinforcement.
Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Silylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthioca Vamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxy Silylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like. Among these, bis (( - triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropyl benzothiazyl tetrasulfide are preferable.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  In the rubber composition of the present invention, the amount of the preferred silane coupling agent varies depending on the type of the silane coupling agent, but is preferably selected in the range of 2 to 20 parts by mass with respect to 100 parts by mass of silica. The If this amount is less than 2 parts by mass, the effect as a coupling agent is hardly exhibited, and if it exceeds 20 parts by mass, the rubber component may be gelled. From the viewpoints of the effect as a coupling agent and the prevention of gelation, the preferred amount of the silane coupling agent is in the range of 5 to 15 parts by mass with respect to 100 parts by mass of silica.

(Other ingredients)
In the rubber composition of the present invention, various chemicals commonly used in the rubber industry, for example, a vulcanization accelerator, a scorch inhibitor, zinc white, stearic acid, etc., if desired, within a range where the object of the present invention is not impaired. Can be contained.
The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include thiazoles such as M (2-mercaptobenzothiazole) and DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2). -Benzothiazolylsulfenamide), TBBS (N- (tert-butyl) -2-benzothiazolylsulfenamide), DZ (N, N-dicyclohexyl-2-benzothiazolylsulfenamide), NOBS (N -Oxydiethylene-2-benzothiazolylsulfenamide) and other sulfenamides, or guanidine-based vulcanization accelerators such as DPG (1,3-diphenylguanidine) and the like. , 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component (total mass of matrix and domain) Preferred, more preferably from 0.2 to 3.0 parts by weight.

  Examples of the antioxidant include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine], AW (6- Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, etc. However, a rubber composition containing an anti-aging agent is used as a tire surface member. When used in the above, the tire surface may turn brown, and the rubber composition according to the present invention has high ozone resistance even when the amount of the anti-aging agent is smaller than that of the conventional composition.

[Method for Producing Rubber Composition of the Present Invention]
The rubber composition of the present invention can be prepared by kneading each compounding component using a kneading machine such as a Banbury mixer, a roll, or an internal mixer. In order to make a chemical bond exist at the interface between the matrix and the domain after vulcanization, it is preferable to add an organic peroxide crosslinking agent in addition to the usual sulfur crosslinking agent.
The rubber composition of the present invention thus prepared can greatly improve the ozone resistance of a tire, particularly a pneumatic tire.

[tire]
In the tire of the present invention, particularly a pneumatic tire, it is possible to significantly improve ozone resistance by using the rubber composition of the present invention described above as at least one member of a sidewall surface layer member and a tread grounding member. From the viewpoint of making it.
The tire of the present invention is manufactured by a usual method. That is, if necessary, the rubber composition of the present invention containing various chemicals as described above is extruded into a sidewall surface layer member and / or a tread member at an unvulcanized stage to form a tire. It is pasted and molded by a normal method on the machine, and a green tire is molded. The green tire is heated and pressed in a vulcanizer to obtain a tire.
As the gas filled in the tire, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen can be used.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. Various measurements and evaluation methods were performed based on the following methods.

(1) Ozone resistance (weather resistance) and tea modification Ozone resistance was measured according to JIS K 6259. About the sample of vulcanized rubber obtained in each Example and Comparative Example, a test piece of 20 mm × 100 mm × 1.0 mm was used, and immediately after the surface was cleaned with acetone, while giving a dynamic elongation of 30%, The test piece subjected to the above treatment was photographed by leaving it in a constant temperature bath having an ozone concentration of 50 pphm for 100 hours.
From the obtained image, the ratio of the area of the crack to the whole sample was calculated, and normalized as Comparative Example 4 being 100. When there is no crack, it is 0, and the smaller the value, the higher the ozone resistance. In addition, if it is 55 or less as ozone resistance, the ozone resistance performance of a tire will fully be exhibited. The evaluation results are shown in Tables 1 and 2.
Further, the sample tea modification after standing for 100 hours was also judged visually. The evaluation results are shown in Tables 1 and 2.

(2) Crack growth resistance (constant strain)
About the sample of vulcanized rubber obtained in each Example and Comparative Example, a 0.5 mm crack was put in the center part of the JIS No. 3 test piece, and fatigue was repeatedly given at a constant strain of 0 to 60% at 60 ° C. The number of times until cutting was measured and evaluated.
The evaluation is expressed as an index when Comparative Example 4 is set to 100, and the larger the index value, the better the crack growth resistance (constant strain). The evaluation results are shown in Tables 1 and 2. If the index value is 80 or more, the crack growth resistance of the tire is sufficient.

(Preparation of ethylene-butadiene copolymer (EBR))
After adding 200 g of a toluene solution to a fully dry 1 L pressure resistant stainless steel reactor, ethylene was introduced at 1.5 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 55.1 μmol in a glass container in a glove box under a nitrogen atmosphere. , 61 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 0.80 mL of diisobutylaluminum hydride were charged and dissolved in 20 mL of toluene to obtain a catalyst solution. Next, the catalyst solution was taken out from the glove box, and the whole amount was added to the polymerization solution. Thereafter, a toluene solution containing 1,3-butadiene was continuously added at a rate of 2 g / min in terms of 1,3-butadiene for 156 minutes, followed by further polymerization for 10 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain an ethylene-butadiene copolymer (EBR). The yield of EBR obtained was 92 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 3.2. The ethylene content was 19 mol% (butadiene content was 81 mol%).
The block polyethylene melting temperature (DSC peak temperature) was 109 ° C., and the chain structure was a block.

Examples 1-4 and Comparative Examples 1-7
Based on each formulation shown in Tables 1 and 2, after performing a master batch kneading step for 3 minutes at a starting temperature of 110 ° C. and a rotation speed of 70 rpm using a Banbury mixer, zinc oxide, a vulcanization accelerator, sulfur and a bond The agent was kneaded in the final kneading step to prepare rubber compositions of the examples and comparative examples.
Each rubber composition obtained was vulcanized under vulcanization conditions at 160 ° C. for 20 minutes to prepare predetermined test pieces, and then evaluated for ozone resistance and crack growth resistance. The results are shown in Tables 1 and 2.

[note]
* 1: Polybutadiene: Polybutadiene rubber manufactured by JSR Corporation, trade name “BR01”
* 2: Polyethylene: Polyethylene rubber manufactured by Nippon Polyethylene Co., Ltd., trade name “KS340T”
* 3: Carbon Black: Tokai Carbon Co., Ltd., trade name “Seast F”
* 4: Vulcanization accelerator a: Di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller DM-P”
* 5: Vulcanization accelerator b: N- (tert-butyl) -2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller NS-P”
* 6: Organic peroxide: Dicumyl peroxide (purity 40% by mass), manufactured by NOF Corporation, trade name “Park Mill D-40”
* 7: Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd.), trade name “NOCRACK 6C”

  In particular, in tires, improvement in ozone resistance is eagerly desired. As is apparent from Tables 1 and 2, it contains a conjugated diene compound-nonconjugated olefin copolymer, a nonconjugated olefin polymer, and a binder. It can be seen that the ozone resistance performance is greatly improved while maintaining the crack growth performance required for the tire.

  The rubber composition of the present invention can greatly improve the ozone resistance of tires, particularly pneumatic tires, so that it is used for passenger cars (including light passenger cars), light trucks, trucks and buses, and off-the-road tires ( It is preferably used for various tires (for construction vehicles, mining vehicles), particularly for a pneumatic tire sidewall member, tread grounding member, etc., particularly for a passenger tire pneumatic tire member and tread grounding. It is suitably used for member parts.

Claims (6)

A rubber composition comprising a polymer component having a conjugated diene compound-nonconjugated olefin copolymer and a nonconjugated olefin polymer, and a binder,
A rubber composition comprising the non-conjugated olefin polymer in an amount of 10% by mass or more based on a polymer component.   The rubber composition according to claim 1, wherein the binder is a free radical generator.   The rubber composition according to claim 2, wherein the free radical generator is at least one selected from a peroxide and an azo polymerization initiator.   The rubber composition according to any one of claims 1 to 3, wherein the conjugated diene compound in the conjugated diene compound-nonconjugated olefin copolymer is a diene rubber containing at least one of polybutadiene and polyisoprene.   The rubber composition according to any one of claims 1 to 4, wherein the non-conjugated olefin polymer is an olefin polymer containing at least one selected from polyethylene, polypropylene, and polybutene.   A tire provided with the member which has a rubber composition of any one of Claims 1-5.