JP2019214680A - Rubber composition, tire, and rubber article - Google Patents

Abstract

To provide a rubber composition capable of achieving both elastic modulus and fracture characteristics after crosslinking at a high level.SOLUTION: The rubber composition contains: a rubber component containing a multi-component copolymer which contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit; and 30-70 pts.mass of silica based on 100 pts.mass of the rubber component. The silica has a CTAB adsorption specific surface area of 170 m/g or more. The silica preferably has a BET specific surface area of 200 m/g or more.SELECTED DRAWING: None

Description

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

In general, rubber compositions used for manufacturing rubber articles such as tires, conveyor belts, anti-vibration rubber, and anti-vibration rubber are required to have high durability and low heat generation. Various rubber components and rubber compositions have been developed.
For example, Patent Document 1 discloses a conjugated diene compound in which the cis-1,4 bond content of the conjugated diene portion (the portion derived from the conjugated diene compound) is greater than 70.5 mol% and the content of the non-conjugated olefin is 10 mol% or more. A copolymer with a non-conjugated olefin compound is disclosed, and it is disclosed that this copolymer is used for a rubber having good performance such as crack growth resistance.

  However, in the technique of Patent Document 1, since the copolymer is a binary copolymer obtained by polymerizing one kind of conjugated diene compound and one kind of non-conjugated olefin compound, When the chain length of the portion where the derived units are continuous, particularly when the ethylene is used, the chain length of the portion where the ethylene-derived units are continuous becomes longer and the crystallinity is increased, so that further improvement in durability is required. was there.

  Therefore, in the technique of Patent Document 2, in a rubber composition, a multi-component copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit in which a structure and physical properties are optimized. In order to improve durability, a technique has been disclosed.

International Publication No. 2012/014455 International Publication No. 2015/1900072

According to the technology of Patent Document 1 described above, when the multi-component copolymer is subjected to a large strain, it can exhibit an energy dissipation effect. Therefore, when the rubber composition is applied to a tire, excellent durability such as improvement in abrasion resistance is obtained. Can be realized.
However, the rubber composition obtained by the technique of Patent Document 1 still has room for improvement in terms of the elastic modulus after crosslinking and the breaking characteristics (tensile strength, etc.), and further improvement has been desired. .

Accordingly, an object of the present invention is to provide a rubber composition that can solve the above-mentioned problems of the conventional technology and can realize excellent durability, and can also achieve a high level of elasticity after crosslinking and fracture characteristics at a high level. .
Another object of the present invention is to provide a tire having both high steering stability and high breaking characteristics, and a rubber article having excellent durability.

  The gist configuration of the present invention for solving the above problems is as follows.

The rubber composition of the present invention has a rubber component containing a multicomponent copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and 30 to 70 parts by mass relative to 100 parts by mass of the rubber component. And silica, wherein the silica has a CTAB adsorption specific surface area of 170 m ² / g or more.
Such a rubber composition of the present invention can realize excellent durability, and at the same time, can achieve both the elastic modulus after crosslinking and the breaking characteristics at a high level.

In the rubber composition of the present invention, the silica preferably has a BET specific surface area of 200 m ² / g or more. In this case, more excellent durability can be realized, and both the elastic modulus after crosslinking and the breaking characteristics can be achieved at a higher level.

In the rubber composition of the present invention, the silica preferably has a CTAB adsorption specific surface area of 190 m ² / g or more. In this case, more excellent durability can be realized, and both the elastic modulus after crosslinking and the breaking characteristics can be achieved at a higher level.

  The rubber composition of the present invention preferably further contains a silane coupling agent in an amount of 3 to 15% by mass based on the content of the silica. In this case, more excellent durability can be realized, and the elasticity after crosslinking and the breaking characteristics can be both compatible at a higher level.

  In the rubber composition of the present invention, the content of the multicomponent copolymer in the rubber component is preferably 70% by mass or more. In this case, more excellent durability can be realized, and the modulus of elasticity and the breaking characteristics after crosslinking can be at a higher level.

  In the rubber composition of the present invention, the multicomponent copolymer has a content of the conjugated diene unit of 1 to 50 mol%, a content of the non-conjugated olefin unit of 40 to 97 mol%, and the aromatic vinyl. The content of the unit is preferably from 2 to 35 mol%. In this case, the durability can be further improved.

  In the rubber composition of the present invention, the multi-component copolymer preferably has an endothermic peak energy of 10 to 150 J / g measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. In this case, workability is improved, and durability after crosslinking can be further improved.

  In the rubber composition of the present invention, the multi-component copolymer preferably has a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter (DSC). In this case, workability is improved, and durability can be further improved.

  In the rubber composition of the present invention, the multi-component copolymer preferably has a glass transition temperature of 0 ° C. or lower measured by a differential scanning calorimeter (DSC). In this case, the workability of the rubber composition is improved.

  In the rubber composition of the present invention, the multi-component copolymer preferably has a crystallinity of 0.5 to 50%. In this case, the workability of the rubber composition is improved, and the durability can be further improved.

  In the rubber composition of the present invention, it is preferable that in the multi-component copolymer, the non-conjugated olefin unit is a non-cyclic non-conjugated olefin unit. In this case, the weather resistance of the rubber composition is improved.

  Here, it is more preferable that the acyclic non-conjugated olefin unit comprises only an ethylene unit. In this case, the weather resistance of the rubber composition is further improved.

  In the rubber composition of the present invention, in the multicomponent copolymer, the aromatic vinyl unit preferably contains a styrene unit. In this case, the weather resistance of the rubber composition is improved.

  In the rubber composition of the present invention, it is preferable that in the multicomponent copolymer, the conjugated diene unit contains a 1,3-butadiene unit and / or an isoprene unit. In this case, the durability and the elastic modulus after crosslinking can be further improved.

The tire of the present invention is characterized by using the above rubber composition or the above rubber composition for a tire.
Such a tire of the present invention can achieve both steering stability and breaking characteristics while having excellent durability.

The rubber article of the present invention is characterized by using the above rubber composition.
Such a rubber article of the present invention is excellent in durability and breaking characteristics.

ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can make the elastic modulus after bridge | crosslinking and a fracture characteristic compatible at a high level can be provided.
Further, according to the present invention, it is possible to provide a tire in which steering stability and breaking characteristics are compatible at a high level, and a rubber article having excellent durability.

  Hereinafter, the rubber composition, the rubber composition for a tire, the tire, and the rubber article of the present invention will be described in detail based on embodiments.

<Rubber composition>
The rubber composition of the present invention comprises a rubber component (a) containing a multicomponent copolymer (a1) containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and the rubber component (a). 30 to 70 parts by mass of silica (b1) with respect to 100 parts by mass,
The silica (b1) has a CTAB adsorption specific surface area of 170 m ² / g or more.

The multi-component copolymer (a1) contained in the rubber composition of the present invention contains a non-conjugated olefin unit, and when greatly distorted, a crystal component derived from the non-conjugated olefin unit collapses, and the energy is increased by the melting energy. Can be dissipated. As a result, the rubber composition of the present invention can realize excellent wear resistance and durability. However, the above-mentioned multi-component copolymer (a1) has a small interaction with carbon black, which is one of the reinforcing fillers (b), and therefore, in a usual composition, it has a high elastic modulus and a high breaking property. It was expected that sufficient effect could not be obtained.
Therefore, in the rubber composition of the present invention, in addition to the durability, the elastic modulus of the rubber composition after cross-linking is increased by including silica (b1) having a high reinforcing property with an appropriate CTAB adsorption specific surface area. As a result, the steering stability when the rubber composition is applied to the tire can be improved, and the breaking characteristics can also be improved.

  The rubber component (a) of the rubber composition of the present invention contains a multicomponent copolymer (a1) containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. The multi-component copolymer (a1) contains at least a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and comprises only a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. And may further contain another monomer unit.

  The conjugated diene unit is a constituent unit derived from a conjugated diene compound as a monomer. The conjugated diene unit enables vulcanization of the multi-component copolymer, and exhibits elongation and strength as a rubber. Here, the conjugated diene compound refers to a conjugated diene compound. The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of such a conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. The conjugated diene compounds may be used alone or in a combination of two or more. The conjugated diene compound as a monomer of the multi-component copolymer is preferably 1,3-butadiene and 1,3-butadiene from the viewpoint of effectively improving the durability of a rubber composition or a tire using the obtained multi-component copolymer. And / or isoprene, more preferably only 1,3-butadiene and / or isoprene, and even more preferably only 1,3-butadiene. Stated another way, the conjugated diene unit in the multi-component copolymer preferably contains 1,3-butadiene units and / or isoprene units, and more preferably consists of only 1,3-butadiene units and / or isoprene units. More preferably, it consists only of 1,3-butadiene units. By increasing the proportion of the 1,3-butadiene unit in the conjugated diene unit, it is possible to increase the affinity for the silica (b1) in the rubber composition. Durability can be obtained. The ratio of the 1,3-butadiene unit in the conjugated diene unit is preferably at least 10% by mass, more preferably at least 15% by mass.

  In the multicomponent copolymer (a1), the content of the conjugated diene unit is preferably 1 mol% or more, more preferably 3 mol% or more, and preferably 50 mol% or less, and 40 mol% or less. %, More preferably 30 mol% or less, even more preferably 25 mol% or less, even more preferably 15 mol% or less. When the content of the conjugated diene unit is at least 1 mol% of the entire multi-component copolymer, a rubber composition and a rubber article having excellent elongation can be obtained, and when it is at most 50 mol%, the weather resistance will be excellent. Further, the content of the conjugated diene unit is preferably in the range of 1 to 50 mol%, more preferably in the range of 3 to 40 mol% of the whole multi-component copolymer.

  The non-conjugated olefin unit is a constituent unit derived from a non-conjugated olefin compound as a monomer. When the non-conjugated olefin unit is greatly distorted, energy is dissipated due to collapse of a crystal component derived from the non-conjugated olefin unit. Here, the non-conjugated olefin compound refers to a compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds. The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of such non-conjugated olefin compounds include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, vinyl pivalate, and 1-phenylthioethene. And heteroatom-substituted alkene compounds such as N-vinylpyrrolidone. The non-conjugated olefin compounds may be used alone or in a combination of two or more. The non-conjugated olefin compound as a monomer of the multi-component copolymer is a non-cyclic non-conjugated olefin compound from the viewpoint of further improving the weather resistance of a rubber composition and a tire using the obtained multi-component copolymer. The non-cyclic non-conjugated olefin compound is more preferably an α-olefin, further preferably an α-olefin containing ethylene, and particularly preferably only ethylene. In other words, the non-conjugated olefin unit in the multi-component copolymer is preferably a non-cyclic non-conjugated olefin unit, and the non-cyclic non-conjugated olefin unit is preferably an α-olefin unit. More preferably, it is an α-olefin unit containing an ethylene unit, and even more preferably, it is composed of only an ethylene unit.

  In the multicomponent copolymer (a1), the content of the non-conjugated olefin unit is preferably at least 40 mol%, more preferably at least 45 mol%, even more preferably at least 55 mol%, It is particularly preferably at least 60 mol%, more preferably at most 97 mol%, even more preferably at most 95 mol%, even more preferably at most 90 mol%. When the content of the non-conjugated olefin unit is 40 mol% or more of the entire multi-component copolymer, the content of the conjugated diene unit or the aromatic vinyl unit is reduced as a result, and the weather resistance is improved, The breaking characteristics (particularly, breaking strength (Tb)) are improved. Further, when the content of the non-conjugated olefin unit is 97 mol% or less, the content of the conjugated diene unit or the aromatic vinyl unit increases as a result, and the breaking characteristics at high temperature (particularly, the elongation at break (Eb)) are increased. improves. In addition, the content of the non-conjugated olefin unit is preferably in the range of 40 to 97 mol%, more preferably in the range of 45 to 95 mol%, and still more preferably in the range of 55 to 90 mol% of the entire multi-component copolymer.

The aromatic vinyl unit is a constituent unit derived from an aromatic vinyl compound as a monomer. The aromatic vinyl unit improves the workability of the multi-component copolymer. Here, the aromatic vinyl compound refers to an aromatic compound substituted with at least a vinyl group, and is not included in the conjugated diene compound. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Such aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. . The aromatic vinyl compound may be used alone or in a combination of two or more. The aromatic vinyl compound as a monomer of the multi-component copolymer preferably contains styrene from the viewpoint of improving the weather resistance of a rubber composition and a tire using the obtained multi-component copolymer, and styrene. More preferably, it consists of only In other words, the aromatic vinyl unit in the multi-component copolymer preferably contains a styrene unit, and more preferably consists of only a styrene unit.
Note that the aromatic ring in the aromatic vinyl unit is not included in the main chain of the multi-component copolymer unless it is bonded to an adjacent unit.

  In the multicomponent copolymer (a1), the content of the aromatic vinyl unit is preferably 2 mol% or more, more preferably 3 mol% or more, and further preferably 35 mol% or less, It is more preferably at most 30 mol%, more preferably at most 25 mol%. When the content of the aromatic vinyl unit is 2 mol% or more, the breaking characteristics at high temperatures are improved. When the content of the aromatic vinyl unit is 35 mol% or less, the effect of the conjugated diene unit and the non-conjugated olefin unit becomes remarkable. In addition, the content of the aromatic vinyl unit is preferably in the range of 2 to 35 mol%, more preferably in the range of 3 to 30 mol%, and still more preferably in the range of 3 to 25 mol% of the whole multi-component copolymer.

  There are no particular restrictions on the number of types of monomers of the multicomponent copolymer (a1) as long as the multicomponent copolymer contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. The multi-component copolymer (a1) may have other constituent units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit. From the viewpoint of obtaining the effect of the above, the content is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less of the entire multi-component copolymer, and it does not contain, that is, the content Is particularly preferably 0 mol%.

  The above-mentioned multi-component copolymer (a1) is, as a monomer, one kind of a conjugated diene compound, one kind of a non-conjugated olefin compound, and one kind of an aromatic compound, from the viewpoint of making abrasion resistance, weather resistance and crystallinity preferable. It is preferably a polymer obtained by polymerizing at least a vinyl compound. In other words, the multi-component copolymer (a1) is preferably a multi-component copolymer containing one kind of conjugated diene unit, one kind of non-conjugated olefin unit, and one kind of aromatic vinyl unit. It is more preferable that the terpolymer is composed of only a conjugated diene unit, one kind of non-conjugated olefin unit, and one kind of aromatic vinyl unit, and is composed only of 1,3-butadiene unit, ethylene unit, and styrene unit. More preferably, it is a terpolymer. Here, "a kind of conjugated diene unit" includes conjugated diene units having different bonding modes.

  In the rubber composition of the present invention, the multicomponent copolymer (a1) has a content of the conjugated diene unit of 1 to 50 mol%, a content of the non-conjugated olefin unit of 40 to 97 mol%, and the fragrance. It is preferable that the content of the vinyl group unit is 2 to 35 mol%. In this case, the wear resistance and weather resistance of the rubber composition are further improved, and by applying to the tire, the wear resistance of the tire can be further improved.

  The multi-component copolymer (a1) preferably has a weight average molecular weight (Mw) in terms of polystyrene of 10,000 to 10,000,000, more preferably 100,000 to 9,000,000. , 150,000 to 8,000,000. When the Mw of the multi-component copolymer is 10,000 or more, the mechanical strength of the rubber composition can be sufficiently ensured, and when the Mw is 10,000,000 or less, high workability can be obtained. Sex can be maintained.

  The multi-component copolymer (a1) preferably has a polystyrene-equivalent number average molecular weight (Mn) of 10,000 to 10,000,000, more preferably 50,000 to 9,000,000. , 100,000 to 8,000,000. When the Mn of the multi-component copolymer is 10,000 or more, the mechanical strength of the rubber composition can be sufficiently ensured, and when the Mn is 10,000,000 or less, high workability can be ensured. Sex can be maintained.

  The multi-component copolymer (a1) has a molecular weight distribution [Mw / Mn (weight average molecular weight / number average molecular weight)] of preferably 4.00 or less, more preferably 3.50 or less, and more preferably 3.50 or less. More preferably, it is not more than 00. When the molecular weight distribution of the multi-component copolymer is 4.00 or less, sufficient physical properties of the multi-component copolymer can be obtained.

  The above-mentioned weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) are determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

In the rubber composition of the present invention, the melting point of the multicomponent copolymer (a1) measured by a differential scanning calorimeter (DSC) is preferably from 30 to 130 ° C, more preferably from 30 to 110 ° C. . When the melting point of the multi-component copolymer (a1) is 30 ° C. or more, the crystallinity of the multi-component copolymer (a1) is increased, the wear resistance of the rubber composition is further improved, and the durability after crosslinking is further improved. Can be improved. When the melting point of the multi-component copolymer (a1) is 130 ° C. or lower, the workability of the rubber composition is improved.
Here, the melting point is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has an endothermic peak energy of 10 to 150 J / g measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C, and 30 to 150 J / g. More preferably, it is 120 J / g. When the endothermic peak energy of the multi-component copolymer (a1) is 10 J / g or more, the crystallinity of the multi-component copolymer (a1) is increased, the abrasion resistance of the rubber composition is further improved, and the durability after crosslinking is improved. Properties can be further improved. When the endothermic peak energy of the multi-component copolymer (a1) is 150 J / g or less, the workability of the rubber composition is improved.
Here, the endothermic peak energy is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a glass transition temperature (Tg) of 0 ° C. or lower measured by a differential scanning calorimeter (DSC), and is preferably -100 to −10 ° C. Is more preferable. When the glass transition temperature of the multicomponent copolymer (a1) is 0 ° C. or lower, the workability of the rubber composition is improved.
Here, the glass transition temperature is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) has a crystallinity of preferably 0.5 to 50%, more preferably 3 to 45%, and more preferably 5 to 45%. It is even more preferred. When the crystallinity of the multi-component copolymer (a1) is 0.5% or more, the crystallinity caused by the non-conjugated olefin unit is sufficiently ensured, the wear resistance of the rubber composition is further improved, and the crosslinking is performed. Later durability can be further improved. When the crystallinity of the multi-component copolymer (a1) is 50% or less, the workability at the time of kneading the rubber composition is improved, and the rubber composition containing the multi-component copolymer (a1) is mixed. Since the tackiness of the rubber composition of the present invention is improved, the workability when rubber members made from the rubber composition are adhered to each other to form a rubber article such as a tire is also improved.
Here, the crystallinity is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a main chain composed of only an acyclic structure. Thereby, the wear resistance of the rubber composition can be further improved, and the durability after crosslinking can be further improved.
In addition, NMR is used as a main measuring means for confirming whether or not the main chain of the multi-component copolymer (a1) has a cyclic structure. Specifically, when a peak derived from a cyclic structure existing in the main chain (for example, a peak appearing at 10 to 24 ppm for a three-membered to five-membered ring) is not observed, the main chain of the multi-component copolymer is , Consisting of only an acyclic structure.

The multi-component copolymer (a1) can be produced through a polymerization step using a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound as monomers, and further, if necessary, a coupling step and a washing step. Steps and other steps may be performed.
Here, in the production of the multi-component copolymer (a1), only a non-conjugated olefin compound and an aromatic vinyl compound are added without adding a conjugated diene compound in the presence of a polymerization catalyst, and these are polymerized. Is preferred. In particular, when the catalyst composition described below is used, since the conjugated diene compound has higher reactivity than the non-conjugated olefin compound and the aromatic vinyl compound, the non-conjugated olefin compound and / or It is easy to polymerize the aromatic vinyl compound. It is also difficult to polymerize the conjugated diene compound first, and then polymerize the non-conjugated olefin compound and the aromatic vinyl compound additionally, because of the characteristics of the catalyst.

  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. When a solvent is used in the polymerization reaction, the solvent may be any solvent that is inert in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

  The polymerization step may be performed in one stage, or may be performed in two or more stages. The one-stage polymerization step includes all kinds of monomers to be polymerized, that is, conjugated diene compounds, non-conjugated olefin compounds, aromatic vinyl compounds, and other monomers, preferably conjugated diene compounds, non-conjugated In this step, the olefin compound and the aromatic vinyl compound are simultaneously reacted and polymerized. In addition, the multi-stage polymerization step means that a part or all of one or two kinds of monomers are first reacted to form a polymer (first polymerization step), and then the remaining kinds of monomers are formed. And one or more steps (second polymerization step to final polymerization step) of adding and remaining one or two kinds of monomers to carry out polymerization. In particular, in the production of a multicomponent copolymer, it is preferable to carry out the polymerization step in multiple stages.

In the polymerization step, the polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably a nitrogen gas or an argon gas. The polymerization temperature of the above polymerization reaction is not particularly limited, but is preferably, for example, in the range of -100 ° C to 200 ° C, and may be about room temperature. The pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound into the polymerization reaction system. In addition, the reaction time of the polymerization reaction is not particularly limited, and is preferably, for example, in the range of 1 second to 10 days, but can be appropriately selected depending on conditions such as the type of polymerization catalyst and polymerization temperature.
In the step of polymerizing the conjugated diene compound, the polymerization may be stopped by using a polymerization terminator such as methanol, ethanol, or isopropanol.

  The polymerization step is preferably performed in multiple stages. More preferably, a first step of mixing a first monomer raw material containing at least an aromatic vinyl compound and a polymerization catalyst to obtain a polymerization mixture, and for the polymerization mixture, a conjugated diene compound, a non-conjugated olefin compound and And a second step of introducing a second monomer material containing at least one selected from the group consisting of aromatic vinyl compounds. More preferably, the first monomer material does not contain a conjugated diene compound, and the second monomer material contains a conjugated diene compound.

  The first monomer raw material used in the first step may contain a non-conjugated olefin compound together with the aromatic vinyl compound. Further, the first monomer raw material may contain the entire amount of the aromatic vinyl compound to be used, or may contain only a part thereof. Further, the non-conjugated olefin compound is contained in at least one of the first monomer material and the second monomer material.

  The first step is preferably performed in an atmosphere of an inert gas, preferably a nitrogen gas or an argon gas, in the reactor. The temperature (reaction temperature) in the first step is not particularly limited, but is preferably, for example, in the range of -100 ° C to 200 ° C, and may be about room temperature. The pressure in the first step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently take the aromatic vinyl compound into the polymerization reaction system. The time (reaction time) spent in the first step can be appropriately selected depending on conditions such as the type of polymerization catalyst and reaction temperature. For example, when the reaction temperature is 25 to 80 ° C., 5 minutes A range of up to 500 minutes is preferred.

  In the first step, as a polymerization method for obtaining a polymerization mixture, 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. When a solvent is used in the polymerization reaction, any solvent may be used as long as it is inert in the polymerization reaction, and examples thereof include toluene, cyclohexanone, and normal hexane.

The second monomer material used in the second step may be a conjugated diene compound alone, or a conjugated diene compound and a non-conjugated olefin compound, or a conjugated diene compound and an aromatic vinyl compound, or a conjugated diene compound or a non-conjugated olefin. Compounds and aromatic vinyl compounds are preferred.
In the case where the second monomer material contains at least one selected from the group consisting of a non-conjugated olefin compound and an aromatic vinyl compound in addition to the conjugated diene compound, these monomer materials are previously dissolved in a solvent or the like. May be introduced into the polymerization mixture after mixing together, or each monomer raw material may be introduced from a single state. Further, each monomer raw material may be added simultaneously or sequentially. In the second step, the method of introducing the second monomer raw material into the polymerization mixture is not particularly limited, but the flow rate of each monomer raw material is controlled to continuously add the second monomer raw material to the polymerization mixture. (So-called metering) is preferable. Here, when a monomer material that is gaseous under the conditions of the polymerization reaction system (for example, ethylene or the like as a non-conjugated olefin compound under the conditions of room temperature and normal pressure) is used, the polymerization reaction system is subjected to a predetermined pressure. Can be introduced.

The second step is preferably performed in an atmosphere of an inert gas, preferably a nitrogen gas or an argon gas, in the reactor. The temperature (reaction temperature) in the second step is not particularly limited. When the reaction temperature is increased, the selectivity of cis-1,4 bond in the conjugated diene unit may decrease. The pressure in the second step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate a monomer such as a conjugated diene compound into the polymerization reaction system. The time (reaction time) spent in the second step can be appropriately selected depending on conditions such as the type of the polymerization catalyst and the reaction temperature, but is preferably, for example, in the range of 0.1 hour to 10 days.
In the second step, the polymerization reaction may be stopped by using a polymerization terminator such as methanol, ethanol, or isopropanol.

Here, the polymerization step of the conjugated diene compound, the non-conjugated olefin compound, and the aromatic vinyl compound includes a step of polymerizing various monomers in the presence of at least one of the following components (A) to (F). It is preferred to include. In the polymerization step, it is preferable to use one or more of the following components (A) to (F) as a catalyst component. It is more preferred to use
(A) Component: Rare earth element compound or reaction product of the rare earth element compound and Lewis base (B) Component: Organometallic compound (C) Component: Aluminoxane (D) Component: Ionic compound (E) Component: Halogen compound ( Component F): substituted or unsubstituted cyclopentadiene (compound having cyclopentadienyl group), substituted or unsubstituted indene (compound having indenyl group), and substituted or unsubstituted fluorene (compound having fluorenyl group) ) (Hereinafter, may be simply referred to as “cyclopentadiene skeleton-containing compound”).
Hereinafter, the components (A) to (F) will be described in detail.

  Examples of the rare earth element compound or a reaction product of the rare earth element compound and a Lewis base (component (A)) include a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base having a rare earth element-carbon bond (hereinafter, referred to as a reaction product of the Lewis base). , "(A-1) component"), a rare earth element compound having no rare earth element-carbon bond, or a reaction product of the rare earth element compound and a Lewis base (hereinafter, also referred to as "(A-2) component"). ).

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

［式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ’は、水素原子、ハロゲン原子、アルコキシ基、チオラート基、アミノ基、シリル基又は炭素数１〜２０の一価の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す］で表されるメタロセン錯体、並びに下記一般式（ＩＩＩ）：

［式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシ基、チオラート基、アミノ基、シリル基又は炭素数１〜２０の一価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が挙げられる。 As the component (A-1), for example, the following general formula (I):

[ ^Wherein , M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represent an alkyl group having 1 to 3 carbon atoms. L represents a neutral Lewis base, w represents an integer of 0 to 3], and a metallocene complex represented by the following general formula (II):

[ ^Wherein M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents unsubstituted or substituted indenyl, and X ′ represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group. , A silyl group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3], a metallocene complex represented by the following general formula: Formula (III):

[ ^Wherein , M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, X represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group. , An amino group, a silyl group or a monovalent 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 Which shows a coordinating anion].

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R of the 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 to 7 or 0 to 11. Preferably, Rs are each independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, and silyl Si.The metalloid group preferably has a hydrocarbyl group. The same is true. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. Note that the two Cp ^R in the general formulas (I) and (II) may be the same or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that

［式中、Ｒは水素原子、メチル基又はエチル基を示す。］ In the general formula (III), Cp ^{R ′} having the above cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _{5-x Rx} . Here, X is an integer of 0-5. Preferably, Rs are each independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, and silyl Si.The metalloid group preferably has a hydrocarbyl group. The same is true. 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.

[Wherein, R represents a hydrogen atom, a methyl group or an ethyl group. ]

In formula (III), Cp ^{R ′} having the above-mentioned indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in} formulas (I) and (II), and preferred examples 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. Preferably, Rs are each independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, and silyl Si.The metalloid group preferably has a hydrocarbyl group. The same is true. 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 elements may be used. Preferable examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (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. Further, 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 a non-conjugated olefin compound or an aromatic vinyl compound is introduced. It will be easier. 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. Further, as the alkyl group, a methyl group is preferable.

The metallocene complex represented by the general formula (II) contains 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 alkoxy group, a thiolate group, an amino group, a silyl group and a monovalent hydrocarbon group having 1 to 20 carbon atoms. . Here, the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a chlorine atom or a bromine atom.

  In formula (III), the alkoxy group represented by X includes a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and the like; 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6 And aryloxy groups such as -neopentylphenoxy group and 2-isopropyl-6-neopentylphenoxy group. Of these, 2,6-di-tert-butylphenoxy group is preferable.

  In formula (III), examples of the thiolate group represented by X include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thion-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, and 2,4,6-triisopropylthiophenoxy group. Among them, 2,4,6-triisopropylthiophenoxy It is preferred.

  In the general formula (III), the amino group represented by X includes an aliphatic amino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; a phenylamino group, a 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl- Arylamino groups such as 6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; and among them, bistrimethylsilyl Amino groups are preferred.

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

  In the general formula (III), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Linear or branched aliphatic hydrocarbon groups such as isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatic hydrocarbons such as phenyl group, tolyl group and naphthyl group Groups; aralkyl groups such as benzyl group; hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group; and among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl And the like.

  In the general formula (III), X is preferably a bistrimethylsilylamino group or a monovalent 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. As the tetravalent boron anion, specifically, 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, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complexes represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) further contain 0 to 3, preferably 0 to 1, neutral Lewis. Contains 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 contains a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  The metallocene complexes represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) may be present as a monomer, and may be a dimer. Alternatively, it may be present as a multimer of more.

［式中、Ｘ’’はハライドを示す。］ The metallocene complex represented by the general formula (I) can be obtained, for example, by adding a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent to an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). ) It can be obtained by reacting with an amine salt (for example, potassium salt or lithium salt). Since the reaction temperature may be about room temperature, the reaction can be carried out under mild conditions. The reaction time is optional, 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, and for example, toluene may be used. Hereinafter, a reaction example for obtaining the metallocene complex represented by the general formula (I) will be described.

[Wherein, X ″ represents a halide. ]

［式中、Ｘ’’はハライドを示す。］ The metallocene complex represented by the general formula (II) may be, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, a potassium salt or a lithium salt) and a silyl salt (for example, , Potassium salt or lithium salt). Since the reaction temperature may be about room temperature, it can be produced under mild conditions. The reaction time is optional, 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 materials and products, and for example, toluene may be used. Hereinafter, a reaction example for obtaining the metallocene complex represented by the general formula (II) will be described.

[Wherein, 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 alkoxy group, a thiolate group, an amino group, a silyl group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents Shows an integer of 0 to 3. 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 triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Specific examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl) ) Carbonium cation and the like. Examples of the amine cation 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, an N, N-dialkylanilinium cation or a carbonium cation is preferable, and an N, N-dialkylanilinium cation is particularly preferable.

The general formula for the reaction [A] ⁺ [B] ^- As the ionic compound represented by a compound of a combination selected from each non-coordinating anion and cation of the, N, N-Jimechiruaniri Preference is given to, for example, potassium tetrakis (pentafluorophenyl) borate and triphenylcarboniumtetrakis (pentafluorophenyl) borate. 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, the mol of 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. A compound represented by the general formula (IV) and an ionic compound represented by the general formula [A] ⁺ [B] ^{− used} in the reaction are separately provided in a polymerization reaction system, and the compound represented by the general formula (III) ) May be formed. Further, by using a metallocene complex represented by the general formula (I) or (II) in combination with an ionic compound represented by the general formula [A] ⁺ [B] ^- , The half metallocene cation complex represented by (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.

Further, as another component (A-1), the following general formula (V):
_{R a MX b QY b ··· (} V)
[Wherein, R represents each independently unsubstituted or substituted indenyl, R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and X represents each independently a carbon atom. X represents a monovalent hydrocarbon group represented by Formulas 1 to 20, X is coordinated to M and Q, Q is an element belonging to Group 13 of the periodic table, and Y is each independently a carbon number 1-20, a monovalent hydrocarbon group or a hydrogen atom, Y is coordinated to Q, and a and b are 2].

［式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系複合触媒を用いることで、多元共重合体を効率良く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、多元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、上記メタロセン系複合触媒を用いない従来の触媒系を用いると、多元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、上記メタロセン系複合触媒を用いない従来の触媒系では、金属触媒に対して１０モル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モル当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 In a preferred example of the metallocene-based composite catalyst, the following general formula (VI):

Wherein, M ¹ is a lanthanoid element, scandium or yttrium, Cp ^R is independently a non-substituted or substituted indenyl, R ^A and R ^B having from 1 to 20 carbon atoms each independently Represents a hydrocarbon group, 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. The metallocene composite catalyst represented by the following formula:
By using the metallocene-based composite catalyst, a multi-component copolymer can be efficiently produced. In addition, by using the metallocene-based composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used in synthesizing the multicomponent copolymer. When a conventional catalyst system that does not use the above metallocene-based composite catalyst is used, it is necessary to use a large amount of alkyl aluminum at the time of synthesizing the multi-component copolymer. For example, in the conventional catalyst system not using the metallocene-based composite catalyst, it is necessary to use 10 mole equivalent or more of alkyl aluminum with respect to the metal catalyst. By adding aluminum, excellent catalytic action is exhibited.

  In the metallocene-based composite catalyst, the metal M in the general formula (V) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these elements may be used. Preferable 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 general formula (V), R is each independently unsubstituted indenyl or substituted indenyl, and R is coordinated to the metal M. Specific examples of the substituted indenyl include, for example, a 1,2,3-trimethylindenyl group, a heptamethylindenyl group, and a 1,2,4,5,6,7-hexamethylindenyl group. .

  In the general formula (V), Q represents an element belonging to Group 13 of the periodic table, and specific examples include boron, aluminum, gallium, indium, and thallium.

  In the above general formula (V), each X independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and a tridecyl group. , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like. The μ-coordination is a coordination mode having a crosslinked structure.

  In the above general formula (V), Y independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and a tridecyl group. , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like.

In the above general formula (VI), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements with atomic numbers 57 to 71, and any of these elements 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 general formula (VI), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R of the 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 to 7 or 0 to 11. Preferably, Rs are each independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, and silyl Si.The metalloid group preferably has a hydrocarbyl group. The same is true. Specific examples of the metalloid group include a trimethylsilyl group.
Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. The two Cp ^R in the formula (VI) may be the same or different from each other.

In the above general formula (VI), R ^A and R ^B each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the R ^A and R ^B are co-ordinated to M ¹ and Al. are doing. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and a tridecyl group. , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like. The μ-coordination is a coordination mode having a crosslinked structure.

In the general formula (VI), R ^C and R ^D are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and a tridecyl group. , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl 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 above-mentioned metallocene-based composite catalyst is prepared, for example, in a solvent by the following general formula (VII):

[ ^Wherein , M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl, and R ^{E to} R ^J each independently represent 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 organic aluminum compound represented by AlR ^K R ^L R ^M And obtained by reacting Since the reaction temperature may be about room temperature, it can be produced under mild conditions. The reaction time is optional, 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 and hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structure analysis.

In the metallocene complex represented by the general formula (VII), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the general formula (VI). In the above formula (VII), 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 (VI).

The metallocene complex represented by the general formula (VII) 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. Further, 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 is facilitated. Further, as the alkyl group, a methyl group is preferable.

  The metallocene complex represented by the general formula (VII) further contains 0 to 3, preferably 0 to 1, neutral 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 contains 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 (VII) may exist as a monomer, or may exist as a dimer or a multimer thereof.

On the other hand, the organoaluminum compound used to produce the metallocene-based composite catalyst is represented by AlR ^K R ^L R ^M, wherein, R ^K and R ^L are hydrocarbon monovalent C1-20 independently 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group and a 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, dioctyl aluminum hydride, di Isooctyl aluminum hydride; ethyl alcohol Mini um dihydride, n- propyl aluminum dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride are preferred. These organoaluminum compounds can be used alone or in combination of two or more. The amount of the organoaluminum compound used for producing the metallocene-based composite catalyst is preferably 1 to 50 times, more preferably about 10 times, the mole of the metallocene complex.

The component (A-2) is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, and has no bond between the 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 rare earth element (M), that is, a lanthanoid element composed of elements having atomic numbers 57 to 71 in the periodic table, or a compound containing scandium or yttrium.
Specific examples of the lanthanoid element include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said component (A-2) 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 rare earth metal salt or complex compound, and one or more coordination selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the compound is a rare earth element compound containing an element. Further, the rare earth element compound or a reaction product of the rare earth element compound and a Lewis base is represented by the following general formula (VIII) or (IX):
M ¹¹ X ¹¹ ₂ · L ¹¹ _w ... (VIII)
M ¹¹ X ¹¹ ₃ · L ¹¹ _w ... (IX)
[In each formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group, an aldehyde residue, Represents a ketone residue, 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].

Examples of the group (ligand) that binds to the rare earth element of the rare earth element compound include a hydrogen atom, a halogen atom, an alkoxy group (a group obtained by removing the hydrogen of a hydroxyl group of an alcohol and forms a metal alkoxide), and a thiolate group ( A group obtained by removing a hydrogen from the thiol group of a thiol compound to form a metal thiolate), an amino group (a group obtained by removing one hydrogen atom bonded to a nitrogen atom of ammonia, a primary amine, or a secondary amine) To form a metal amide), a silyl group, an aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, and a phosphorus compound residue.
Specific examples of the group (ligand) include a hydrogen atom; an aliphatic alkoxy group 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; 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, thion-butoxy group, thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy Aliphatic thiolate group such as a group; thiophenoxy group, 2,6-di-tert-butyl Offenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, Arylthiolate groups such as 2-isopropyl-6-thioneopentylphenoxy group and 2,4,6-triisopropylthiophenoxy group; aliphatic amino groups such as dimethylamino group, diethylamino group and diisopropylamino group; phenylamino group; 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert- Butyl-6-neopentylphenylamino group, Arylamino groups such as -isopropyl-6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; trimethylsilyl group and tris (trimethylsilyl) Silyl groups such as silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, and triisopropylsilyl (bistrimethylsilyl) silyl group; and halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. .
Examples of the group (ligand) further include residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, and 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone and 2′-hydroxybutyrophenone Hydroxyphenone residues such as 2,2'-hydroxypropiophenone; ketone residues (especially diketone residues) such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone and ethylacetylacetone; Herbic 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, pivalic acid, versatic acid [Shell Chem. Co., Ltd. Product name, synthetic acid composed of a mixture of isomers of C10 monocarboxylic acid], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid and succinic acid; hexanethioic acid, 2,2- Thiocarboxylic acid residues such as dimethylbutanethioic acid, decanethioic acid, and thiobenzoic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, and phosphoric acid Bis (1-methylheptyl), 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 (2-ethylhexyl) ) (P-nonylphenyl) and other phosphoric acid ester residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, monoethyl 2-ethylhexylphosphonate Residues of phosphonic esters such as p-nonylphenyl, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate; dibutylphosphinic acid, bis (2-ethylhexyl) phosphine 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-meth L-heptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p- Examples include phosphinic acid residues such as nonylphenylphosphinic acid.
These groups (ligands) may be used alone or in a combination of two or more.

Examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, if the rare earth element compound is reacted with a plurality of Lewis bases (in the general formula (VIII) and (IX), when w is 2 or 3), the Lewis base L ¹¹ may be the same It may be different.

Preferably, the rare earth element compound has the following general formula (X):
M− (AQ ¹ ) (AQ ² ) (AQ ³ ) (X)
Wherein M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur Yes; however, having at least one MA bond]. Here, the lanthanoid element is specifically lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. The compound is a component that can improve the catalytic activity in the reaction system, shorten the reaction time, and increase the reaction temperature.

  As M in the general formula (X), gadolinium is particularly preferable from the viewpoint of enhancing the catalytic activity and the reaction controllability.

When A in the general formula (X) is nitrogen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, NQ ¹ , NQ ² and NQ ³ ) include an amino group. And in this case, it has three MN bonds.

  Examples of the amino group include an aliphatic amino group such as a dimethylamino group, a diethylamino group, and a diisopropylamino group; a phenylamino group, a 2,6-di-tert-butylphenylamino group, a 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, An arylamino group such as a 2,4,6-tri-tert-butylphenylamino group; a bistrialkylsilylamino group such as a bistrimethylsilylamino group; and particularly, a solubility in an aliphatic hydrocarbon and an aromatic hydrocarbon. In view of the above, a bistrimethylsilylamino group is preferable. The amino group may be used alone or in combination of two or more.

According to the above configuration, the component (A-2) can be a compound having three MN bonds, each bond is chemically equivalent, and the structure of the compound is stable, so that handling is easy. Become.
With the above configuration, the catalytic activity in the reaction system can be further improved. Therefore, the reaction time can be further shortened, and the reaction temperature can be further increased.

When A in the general formula (X) is oxygen, the rare earth element-containing compound represented by the general formula (X) (that is, M- (OQ ¹ ) (OQ ² ) (OQ ³ )) is particularly limited. Although not shown, for example, the following general formula (XI):
(RO) ₃ M (XI)
And a rare earth alcoholate represented by the following general formula (XII):
(R-CO ₂ ) ₃ M (XII)
And the like.
Here, in the above general formulas (XI) and (XII), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.

When A in the general formula (X) is sulfur, the rare earth element-containing compound represented by the general formula (X) (that is, M- (SQ ¹ ) (SQ ² ) (SQ ³ )) is particularly limited. However, for example, the following general formula (XIII):
(RS) ₃ M (XIII)
And a rare earth alkylthiolate represented by the following general formula (XIV):
(R-CS ₂ ) ₃ M (XIV)
And the like.
Here, in the above general formulas (XIII) and (XIV), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.

The organometallic compound (component (B)) has the following general formula (XV):
YR ¹ _a R ² _b R ³ _c ... (XV)
[Wherein, Y is a metal selected from Group 1 of the periodic table, Group 2, Group 12 and Group 13, and R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is a group 1 in the periodic table A is 1 and b and c are 0 when it is a metal selected from the group consisting of: and a and b when Y is a metal selected from Group 2 and Group 12 of the periodic table. Is 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].

In the general formula (XV), as the hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ , R ² and R ³ , specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Linear or branched aliphatic hydrocarbon groups such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatics such as phenyl group, tolyl group and naphthyl group A hydrocarbon group; an aralkyl group such as a benzyl group; and the like, among which a methyl group, an ethyl group, and an isobutyl group are preferable.

As the component (B), the following general formula (XVI):
AlR ¹ R ² R ³ ... (XVI)
Wherein R ¹ and R ² are a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ May be the same or different from each other.]. The organoaluminum compound corresponds to a compound in which Y is Al and a, b, and c are 1 in the general formula (XV).

  Examples of the organoaluminum compound of the general formula (XVI) 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, diisohexyl aluminum hydride, dioctyl aluminum Hydride, diisooctyl aluminum hydride Ethylaluminum dihydride, n- propyl aluminum dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride are preferred.

  The component (B) can be used alone or in combination of two or more. When the component (B) is used together with the component (A), it is preferably used in an amount of 1 to 50 times, and more preferably about 10 times, the mole of the component (A). preferable.

  The aluminoxane (component (C)) is a compound obtained by contacting an organoaluminum compound with a condensing agent. By using the component (C), the catalytic activity in the polymerization reaction system can be further improved, so that the desired copolymer can be easily obtained. Further, the reaction time can be further shortened, and the reaction temperature can be further increased.

Here, examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Particularly, trimethylaluminum, and a mixture of trimethylaluminum and tributylaluminum are preferable. .
On the other hand, examples of the condensing agent include water and the like.

As the component (C), for example, the following formula (XVII):
− (Al (R ⁷ ) O) _n − (XVII)
Wherein, R ⁷ is a hydrocarbon group having 1 to 10 carbon atoms, wherein a portion of the hydrocarbon group may be substituted by halogen and / or alkoxy group; R ⁷ is between the repeating units May be the same or different; n is 5 or more].
The molecular structure of the aluminoxane may be linear or cyclic.
N in the above formula (XVII) is preferably 10 or more.
Further, as for R ⁷ in the above formula (XVII), examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group and an isobutyl group, and a methyl group is particularly preferable. The hydrocarbon groups may be used alone or in combination of two or more. Regarding R ⁷ in the formula (XVII), the hydrocarbon group is preferably a combination of a methyl group and an isobutyl group.
The aluminoxane preferably has high solubility in aliphatic hydrocarbons, and preferably has low solubility in aromatic hydrocarbons. For example, aluminoxane which is commercially available as a hexane solution is preferable.
Here, examples of the aliphatic hydrocarbon include hexane and cyclohexane.

The component (C) is preferably a compound represented by the following formula (XVIII):
_{- (Al (CH 3) x} (i-C 4 H 9) y O) m - ··· (XVIII)
[Wherein, x + y is 1; m is 5 or more] (hereinafter, also referred to as “TMAO”). As the TMAO, for example, a product name “TMAO-341” manufactured by Tosoh Fine Chemical Co., Ltd. may be mentioned.

In addition, the component (C) is preferably a compound represented by the following formula (XIX):
_{- (Al (CH 3) 0.7} (i-C 4 H 9) 0.3 O) k - ··· (XIX)
[In the formula, k is 5 or more] may be used as the modified aluminoxane (hereinafter, also referred to as “MMAO”). As the MMAO, for example, a product name “MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd. may be mentioned.

Further, the component (C) is preferably a compound represented by the following formula (XX):
-[(CH ₃ ) AlO] _i- (XX)
[Wherein, i is 5 or more] (hereinafter, also referred to as “PMAO”). As the PMAO, for example, a product name “PMAO-211” manufactured by Tosoh Fine Chemical Co., Ltd. may be mentioned.

  The component (C) is preferably MMAO or TMAO among the above-mentioned MMAO, TMAO and PMAO from the viewpoint of enhancing the effect of improving the catalytic activity, and particularly from the viewpoint of further enhancing the effect of improving the catalytic activity. More preferably, it is TMAO.

  As the component (C), one type can be used alone, or two or more types can be used in combination. When the component (C) is used together with the component (A) from the viewpoint of improving the catalytic activity, 10 mol of aluminum in the component (C) is added to 1 mol of the rare earth element in the component (A). It is preferably used so as to be more than, more preferably used so as to be 100 mol or more, and more preferably used so as to be 1000 mol or less, and used so as to be 800 mol or less. Is more preferable.

  The ionic compound (component (D)) comprises a non-coordinating anion and a cation. When the component (D) is used together with the component (A), examples of the component (D) include ionic compounds capable of producing a cationic transition metal compound by reacting with the component (A).

  Here, as the non-coordinating anion, a tetravalent boron anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluoroborate) Phenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl) Phenyl] borate, and tridecahydride-7,8-dicarboundecaborate. Of these, tetrakis (pentafluorophenyl) borate is preferable.

  On the other hand, 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. Specific examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation (also referred to as “trityl cation”) and a tri (substituted phenyl) carbonium cation. More specifically, a tri (methylphenyl) carbonium cation, a tri (dimethylphenyl) carbonium cation and the like can be mentioned. Examples of the amine cation include an ammonium cation. Specific examples of the ammonium cation include trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation). N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; diisopropyl Dialkylammonium cations such as ammonium cation and dicyclohexylammonium cation are exemplified. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, an N, N-dialkylanilinium cation or a carbonium cation is preferable, and an N, N-dialkylanilinium cation is particularly preferable.

  Therefore, as the ionic compound (component (D)), a compound selected and combined from the non-coordinating anions and cations described above is preferable, and specifically, N, N-dimethylanilinium tetrakis (pentafluoro) Phenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferred.

  As the component (D), one type can be used alone, or two or more types can be used in combination. When the component (D) is used together with the component (A), the amount of the component (D) is preferably 0.1 to 10 times, and more preferably about 1 time, based on the component (A). Is more preferred.

  Examples of the halogen compound (component (E)) include a halogen-containing compound that is a Lewis acid (hereinafter, also referred to as “component (E-1)”) and a complex compound of a metal halide and a Lewis base (hereinafter, “(E-1) component”). E-2), an organic compound containing an active halogen (hereinafter, also referred to as a “(E-3) component”), and the like. When the component (E) is used together with the component (A), for example, the component (A) reacts with the component (A) to convert a cationic transition metal compound, a halogenated transition metal compound, or a compound having a transition metal center with insufficient charge. Can be generated.

As the component (E-1), for example, an element belonging to Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14, or Group 15 in the periodic table Can be used. Preferably, an aluminum halide or an organic metal halide is used. Further, as the halogen element, chlorine or bromine is preferable.
As the halogen-containing compound as the Lewis acid, specifically, methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, Diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, tri (pentafluorophenyl Aluminum, tri (pentafluorophenyl) borate, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride and the like. Among these, diethyl aluminum chloride, Ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide and ethyl aluminum dibromide are particularly preferred.
The component (E-1) may be used alone or in combination of two or more.

Examples of the metal halide constituting the component (E-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, and chloride. Barium, 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 and the like. Among them, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferable, and magnesium chloride, chloride Ngan, zinc chloride, copper chloride being particularly preferred.
The Lewis base constituting the component (E-2) is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol, or the like. 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 Oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, and the like, among which tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.
The Lewis base is reacted at a rate of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. The use of a reaction product with this Lewis base can reduce the amount of metal remaining in the polymer.
The component (E-2) may be used alone, or two or more kinds may be used in combination.

  Examples of the component (E-3) include benzyl chloride.

  The component (E) can be used alone or in combination of two or more. When the component (E) is used together with the component (A), the amount of the component (E) is preferably 0 to 5 times, and more preferably 1 to 5 times the mol of the component (A). preferable.

  The cyclopentadiene skeleton-containing compound (component (F)) has a group selected from a cyclopentadienyl group, an indenyl group, and a fluorenyl group, and the cyclopentadiene skeleton-containing compound (F) is substituted or unsubstituted. It is at least one compound selected from the group consisting of cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene. As the component (F), one type may be used alone, or two or more types may be used in combination.

  Examples of the substituted or unsubstituted cyclopentadiene include cyclopentadiene, pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene, (1-benzyldimethylsilyl) cyclopenta [l] phenanthrene, and the like. Is mentioned.

  Examples of the substituted or unsubstituted indene include, for example, indene, 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, and 3-benzyl-2-phenyl- 1H-indene, 1-benzyl-1H-indene, 1-methyl-3-dimethylbenzylsilyl-indene, 1,3-bis (t-butyldimethylsilyl) -indene, (1-benzyldimethylsilyl-3-cyclopentyl) Examples include indene and (1-benzyl-3-t-butyldimethylsilyl) indene, and from the viewpoint of reducing the molecular weight distribution, 3-benzyl-1H-indene and 1-benzyl-1H-indene are preferred.

  Examples of the substituted or unsubstituted fluorene include fluorene, trimethylsilylfluorene, and isopropylfluorene.

  In particular, the cyclopentadiene skeleton-containing compound (component (F)) is preferably a substituted cyclopentadiene, a substituted indene or a substituted fluorene, and more preferably a substituted indene. As a result, the bulkiness of the polymerization catalyst is advantageously increased, so that the reaction time can be shortened and the reaction temperature can be increased. In addition, since many conjugated electrons are provided, the catalytic activity in the reaction system can be further improved.

  Here, examples of the substituent of the substituted cyclopentadiene, the substituted indene, and the substituted fluorene include a hydrocarbyl group and a metalloid group, and the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. More preferably, it is 1-8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, and silyl Si.The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the same as the above-mentioned hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  As the component (F), one type can be used alone, or two or more types can be used in combination. From the viewpoint of improving the catalytic activity, the amount of the component (F) used is preferably more than 0 as a molar ratio to the component (A) when used together with the component (A) from the viewpoint of improving the catalytic activity. It is more preferably at least 1, particularly preferably at least 1, further preferably at most 3, more preferably at most 2.5, particularly preferably at most 2.2.

  It is preferable that the above-mentioned components (A) to (F) are variously combined and used as a catalyst composition in the polymerization step. Suitable catalyst compositions include the following first and second catalyst compositions.

  The first catalyst composition includes the component (A-1), the component (B), and the component (D), and further includes, as optional components, the component (C) and the component (E). )) It is preferable to include one or more components. When the component (A-1) is a metallocene composite catalyst represented by the general formula (V), the component (B) is also an optional component.

  The second catalyst composition includes the component (A-2), the component (B), and the component (D), and further includes, as optional components, the component (C) and the component (E). )) And at least one of the components (F). When the second catalyst composition contains the component (F), the catalytic activity is improved.

The coupling step is a step of performing a reaction (coupling reaction) for modifying at least a part (for example, a terminal) of a polymer chain of the multi-component copolymer obtained in the polymerization step.
In the coupling step, the coupling reaction is preferably performed when the polymerization reaction reaches 100%.
The coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a tin-containing compound such as bis (1-octadecyl maleate) dioctyltin (IV); Isocyanate compounds such as 4,4'-diphenylmethane diisocyanate; and alkoxysilane compounds such as glycidylpropyltrimethoxysilane. These may be used individually by 1 type and may use 2 or more types together.
Among these, bis (1-octadecyl maleate) dioctyltin (IV) is preferable in terms of reaction efficiency and low gel formation.
The number average molecular weight (Mn) can be increased by performing a coupling reaction.

The washing step is a step of washing the multi-component copolymer obtained in the polymerization step. The medium used for washing is not particularly limited and may be appropriately selected depending on the intended purpose.Examples include methanol, ethanol, and isopropanol. Can be used by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid, etc.) to these solvents. The amount of the acid to be added is preferably 15 mol% or less based on the solvent. Above this, the acid may remain in the multi-component copolymer and adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of the catalyst residue in the multi-component copolymer can be suitably reduced.

  In the rubber composition of the present invention, the content of the multicomponent copolymer (a1) in the rubber component (a) is not particularly limited, but is preferably 70% by mass or more, and more preferably 80% by mass or more. Is more preferable. When the content of the multi-component copolymer (a1) in the rubber component (a) is 70% by mass or more, the action of the multi-component copolymer (a1) is sufficiently exerted, and the wear resistance of the rubber composition is reduced. As a result, the localization of silica (b1) in the phase of another polymer component can be suppressed, and as a result, the elastic modulus and fracture characteristics of the rubber composition after crosslinking can be further improved.

  The rubber component in the rubber component (a) other than the multi-component copolymer (a1) is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include natural rubber (NR) and isoprene rubber. (IR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber And the like. These may be used alone or as a mixture of two or more.

And the rubber composition of the present invention contains silica (b1), and the silica (b1) has a CTAB adsorption specific surface area of 170 m ² / g or more.
Since the rubber composition contains silica (b1) having a high reinforcing property as the reinforcing filler (b), the reinforcing effect of the rubber composition after crosslinking can be greatly increased. Even when the interaction between the coalesced compound (a1) and the silica (b1) is low, it is possible to achieve both the elastic modulus and the breaking characteristics of the crosslinked rubber composition at a high level.

  The silica (b1) is not particularly limited except that it has the above-mentioned CTAB adsorption specific surface area. For example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate and the like can be used, and among these, wet silica is preferable.

Here, the CTAB adsorption specific surface area of the silica (b1) needs to be 170 m ² / g or more, preferably 180 m ² / g or more, more preferably 190 m ² / g or more. . Since silica having a small particle size can be used, a higher level of both the elastic modulus and the breaking characteristics of the rubber composition after crosslinking can be achieved. The CTAB adsorption specific surface area of the silica (b1) is not particularly limited, but is preferably 350 m ² / g or less. By setting the upper limit of the particle size of the silica, deterioration of the low loss property can be reliably suppressed.
The CTAB adsorption specific surface area (m ² / g) of the silica (b1) was determined based on the external surface area of the silica (b1) including no micropores when CTAB (cetyltrimethylammonium bromide) was adsorbed on the silica. It is indicated by specific surface area and can be measured in accordance with ASTM D3765-92.

The BET specific surface area of the silica (b1) is preferably at least 200 m ² / g, more preferably at least 210 m ² / g, and even more preferably at least 230 m ² / g. In order to make the silica surface a surface state advantageous for dispersion, the larger the surface area, the better. By setting the BET specific surface area to 200 m ² / g or more, the unvulcanized viscosity can be reduced, and the low loss property is improved. More excellent elastic modulus and fracture characteristics can be realized.
The BET specific surface area is a specific surface area determined by the BET method, and can be measured in the present invention in accordance with ASTM D4820.

The content of the silica (b1) is not particularly limited, but it is possible to achieve a higher level of both the elastic modulus and the breaking property of the crosslinked rubber composition while reliably suppressing the deterioration of the low loss property. From the viewpoint of being possible, the amount is preferably 5 to 100 parts by mass, more preferably 25 to 45 parts by mass, based on 100 parts by mass of the rubber component (a).
By setting the content of the silica (b1) to 5 parts by mass or more with respect to 100 parts by mass of the rubber component (a), a sufficient elastic modulus and fracture characteristics can be obtained. The content of the rubber component (a) is set to 100 parts by mass or less with respect to 100 parts by mass of the rubber component (a).

The rubber composition of the present invention preferably contains a filler other than the silica (b1) described above (other filler (b2)) as the reinforcing filler (b).
When the rubber composition contains other fillers, the reinforcing property and the low loss property of the rubber composition can be improved. The other filler (b2) is not particularly limited, and may be carbon black, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide. , Titanium oxide, potassium titanate, barium sulfate and the like. Among them, it is preferable to include at least one of silica and aluminum hydroxide, and more preferable to include at least silica. As the other filler (b2), one type may be used alone, or two or more types may be used in combination.

Here, examples of the carbon black include GPF, FEF, HAF, ISAF, and SAF grade carbon black.
Further, as the aluminum hydroxide, it is preferable to use Heidilite (registered trademark, manufactured by Showa Denko KK) or the like.

  The content of the other filler (b2) is not particularly limited and can be appropriately selected depending on the purpose.

Further, the rubber composition of the present invention preferably contains a crosslinking agent (c) when crosslinking.
The crosslinking agent (c) is not particularly limited and can be appropriately selected depending on the purpose. Examples include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, a sulfur compound-based crosslinking agent, and an oxime-nitrosamine-based crosslinking agent. In addition, as a rubber composition for tires, a sulfur-based crosslinking agent (vulcanizing agent) is more preferable among these.
The content of the crosslinking agent (c) is not particularly limited and may be appropriately selected depending on the purpose. However, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component (a).

  When the vulcanizing agent (c) is used, a vulcanization accelerator (d) can be used in combination. Examples of the vulcanization accelerator (d) include compounds such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate, and xanthate compounds. Can be

  The rubber composition of the present invention preferably contains a resin component (e) as necessary. When the rubber composition contains the resin component (e), the workability of the rubber composition is further improved. In addition, since the rubber composition contains the resin component (e) together with the multi-component copolymer (a1), high abrasion resistance derived from the multi-component copolymer (a1) is maintained, and molding of tires and the like is performed. In some cases, a rubber composition having excellent tackiness when adhering to another member can be provided, which leads to improvement in productivity of tires and the like.

  As the resin component (e), various natural resins and synthetic resins can be used. Specifically, rosin-based resins, terpene-based resins, petroleum-based resins, phenol-based resins, coal-based resins, xylene-based resins It is preferable to use a resin or the like. These resin components (e) may be used alone or in combination of two or more.

  In the natural resin, examples of the rosin-based resin include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin glycerin, and pentaerythritol ester.

In the natural resin, examples of the terpene-based resin include terpene resins such as α-pinene-based, β-pinene-based, and dipentene-based resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated terpene resins.
Among these natural resins, a polymerized rosin, a terpene phenol resin, and a hydrogenated terpene resin are preferable from the viewpoint of abrasion resistance of the compounded rubber composition.

In the synthetic resin, a petroleum-based resin is, for example, a cracked oil fraction containing unsaturated hydrocarbons such as olefins and diolefins by-produced together with petrochemical basic raw materials such as ethylene and propylene by pyrolysis of naphtha of Petrochemical Industry. Can be obtained as a mixture by polymerization with a Friedel Crafts type catalyst. Examples of the petroleum resin include an aliphatic petroleum resin obtained by (co) polymerizing a C ₅ fraction obtained by pyrolysis of naphtha (hereinafter, may be referred to as “C ₅ resin”), naphtha. Aromatic petroleum resin (hereinafter sometimes referred to as “C ₉ resin”) obtained by (co) polymerizing a C ₉ fraction obtained by thermal decomposition of the above C ₅ fraction and a C ₉ fraction Petroleum resin (hereinafter sometimes referred to as “C ₅ -C ₉ resin”) obtained by copolymerization of components, alicyclic compound-based petroleum resins such as hydrogenated and dicyclopentadiene-based resins And styrene-based resins such as styrene, substituted styrene or copolymers of styrene and other monomers.

The C ₅ fraction obtained by thermal cracking of naphtha, usually 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-olefin such as butene Examples include hydrocarbons, diolefin-based hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene. The aromatic petroleum resin obtained by (co) polymerizing the C ₉ fraction is a resin obtained by polymerizing an aromatic having 9 carbon atoms containing vinyl toluene and indene as main monomers, and is obtained by thermal decomposition of naphtha. Specific examples of the obtained C ₉ fraction include styrene homologues such as α-methylstyrene, β-methylstyrene and γ-methylstyrene, and indene homologues such as indene and cumarone. The trade names include petrozine manufactured by Mitsui Petrochemical, petrolite manufactured by Mikuni Chemical, neopolymer manufactured by Nippon Petrochemical, and petcoll manufactured by Toyo Soda.

Further, in the present invention, from the viewpoint of workability, a modified petroleum resin obtained by modifying the petroleum resin comprising the C ₉ fraction can be suitably used. Examples of the modified petroleum resin, an unsaturated alicyclic compound modified with C ₉ petroleum resins, C ₉ petroleum resins modified with a compound having a hydroxyl group, C ₉ petroleum resins modified with an unsaturated carboxylic acid compound No.

Preferred unsaturated alicyclic compounds include cyclopentadiene, methylcyclopentadiene and the like. As the unsaturated alicyclic compound, a Diels-Alder reaction product of an alkylcyclopentadiene is also preferable, and as a Diels-Alder reaction product of the alkylcyclopentadiene, dicyclopentadiene, cyclopentadiene / methylcyclopentadiene codimer And tricyclopentadiene. As the unsaturated alicyclic compound, dicyclopentadiene is particularly preferred. The dicyclopentadiene-modified C ₉ petroleum resin can be obtained by thermal polymerization or the like in the presence of both dicyclopentadiene and C ₉ fraction. Examples of the dicyclopentadiene-modified C ₉ petroleum resin include Neopolymer 130S (manufactured by Nippon Petrochemical).

In addition, examples of the compound having a hydroxyl group include an alcohol compound and a phenol compound. Specific examples of the alcohol compound include, for example, alcohol compounds having a double bond such as allyl alcohol and 2-butene-1,4 diol. As the phenol compound, alkylphenols such as phenol, cresol, xylenol, p-tert-butylphenol, p-octylphenol, and p-nonylphenol can be used. These compounds having a hydroxyl group may be used alone or in combination of two or more. Further, a C ₉ petroleum resin having a hydroxyl group is obtained by thermally polymerizing an alkyl (meth) acrylate or the like together with a petroleum fraction to introduce an ester group into the petroleum resin, and then reducing the ester group. After the double bond remains or is introduced therein, the compound can be produced by a method of hydrating the double bond, or the like. The C ₉ petroleum resin having a hydroxyl group, can be used those obtained by the various methods as, Performance, viewed from the manufacturing aspect, it is preferred to use a phenol-modified petroleum resins. The phenol-modified petroleum resin is obtained by cationic polymerization of the C ₉ fraction in the presence of phenol, is easily modified, and is inexpensive. Examples of the phenol-modified C ₉ petroleum resin, for example, Neo Polymer E-130 (manufactured by Nippon Petrochemicals).

Furthermore, the modified C ₉ petroleum resin with an unsaturated carboxylic acid compound is capable of modifying the C ₉ petroleum resin in an ethylenically unsaturated carboxylic acid. Representative examples of such ethylenically unsaturated carboxylic acids include maleic anhydride, fumaric acid, itaconic acid, tetrahydro (anhydride) phthalic acid, (meth) acrylic acid, citraconic acid, and the like. The unsaturated carboxylic acid-modified C ₉ petroleum resin can be obtained by thermally polymerizing the C ₉ petroleum resin and the ethylenically unsaturated carboxylic acid. In the present invention, maleic acid-modified C ₉ petroleum resin is preferred. Examples of the unsaturated carboxylic acid-modified C ₉ petroleum resin, for example, Neo Polymer 160 (manufactured by Nippon Petrochemicals).

Further, in the present invention can be suitably used C ₅ fraction and C ₉ fraction copolymer resin obtained by thermal cracking of naphtha. Here, the C ₉ fraction is not particularly limited, but is preferably a C ₉ fraction obtained by pyrolysis of naphtha. Specifically, examples include TS30, TS30-DL, TS35, and TS35-DL of the Struktol series manufactured by SCHILL & SEILACHER.

  In the synthetic resin, examples of the phenolic resin include an alkylphenol formaldehyde resin and a rosin modified product thereof, an alkylphenol acetylene resin, a modified alkylphenol resin, a terpene phenol resin, and the like. Hitachi Chemical Co., Ltd.) and cholecin (manufactured by BASF) of p-tert-butylphenol acetylene resin.

In the synthetic resin, a coal-based resin includes a coumarone indene resin and the like, and in the synthetic resin, a xylene-based resin includes a xylene formaldehyde resin. In addition, other polybutene can be used as the resin component. Among these synthetic resins, from the viewpoint of abrasion resistance of the compounded rubber composition, a copolymer resin of a C ₅ fraction and a C ₉ fraction, and an aromatic resin obtained by (co) polymerizing a C ₉ fraction. Group petroleum resins, phenolic resins and coumarone indene resins are preferred.

The resin component (e) preferably has an SP value of 4 or less, more preferably 3 or less. When the SP value of the resin component (e) is 4 or less, the resin component (e) can be prevented from being locally present in the rubber composition and becoming a destruction nucleus, and the wear resistance of the rubber composition can be reduced. Further improve. The lower limit of the SP value of the resin component (e) is not particularly limited, but is preferably 0.01 or more.
Here, the SP value of the resin component (e) means a solubility parameter calculated using Hansen's formula, and more specifically, among the three parameters of Hansen, the dipole interaction between molecules is specified. It means a numerical value calculated from the action energy and the energy due to hydrogen bonding.

The resin component (e) preferably has a weight average molecular weight (Mw) of 2000 or less, more preferably 1500 or less. When the weight average molecular weight (Mw) of the resin component (e) is 2,000 or less, it is possible to suppress the resin component (e) from being locally present in the rubber composition and becoming a destruction nucleus. The wear resistance is further improved. The lower limit of the weight average molecular weight (Mw) of the resin component (e) is not particularly limited, but is preferably 400 or more.
Here, the weight average molecular weight (Mw) of the resin component (e) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  Further, the resin component (e) is preferably a resin having a softening point of 200 ° C. or lower (measuring method: ASTM E28-58-T), more preferably 80 to 150 ° C., and preferably 90 to 90 ° C. The range of ℃ to 120 ℃ is even more preferred. When the softening point is 200 ° C. or less, the temperature dependency of the hysteresis loss characteristic is small, and the workability is further improved.

  The content of the resin component (e) is preferably from 5 to 150 parts by mass, more preferably from 5 to 100 parts by mass, and more preferably from 10 to 80 parts by mass, based on 100 parts by mass of the rubber component (a). Is more preferable, and a range of 10 to 50 parts by mass is particularly preferable. When the content of the resin component (e) is 5 parts by mass or more based on 100 parts by mass of the rubber component (a), the tackiness and abrasion resistance of the rubber composition are further improved, and 150 parts by mass or less. If so, the workability of the rubber composition can be favorably maintained.

  Further, the rubber composition of the present invention preferably contains a softener (f), if necessary. When the rubber composition contains the softener (f), the workability of the rubber composition is improved.

  Examples of the softener (f) include mineral oils derived from minerals, aromatic oils derived from petroleum, paraffinic oils, naphthenic oils, and palm oils derived from natural products. Among these, a mineral softener and a petroleum softener are preferred from the viewpoint of the abrasion resistance of the rubber composition.

As the softening agent, a mixture of a naphthenic oil and asphalt and a paraffin oil are particularly preferable.
Here, in the mixture of the naphthenic oil and the asphalt, the naphthenic oil may be a hydrogenated naphthenic oil. It can be obtained by chemical purification. On the other hand, asphalt is preferably 5% by mass or less of the asphaltene component from the viewpoint of compatibility with the rubber component (a) and the effect as a softener. The asphaltene component is quantified by a composition analysis measured according to the JPI method (Japan Petroleum Institute method).

The softener (f) preferably has an SP value of 4 or less, more preferably 3 or less. When the SP value of the softener (f) is 4 or less, it is possible to suppress the softener (f) from being locally present in the rubber composition and becoming a breaking nucleus, and the wear resistance of the rubber composition is reduced. Further improve. The lower limit of the SP value of the softener (f) is not particularly limited, but is preferably 0.01 or more.
Here, the SP value of the softener (f) means a solubility parameter calculated using Hansen's formula, and more specifically, among the three parameters of Hansen, the dipole interaction between molecules is defined. It means a numerical value calculated from the action energy and the energy due to hydrogen bonding.

The weight average molecular weight (Mw) of the softener (f) is preferably 2000 or less, more preferably 1500 or less. When the weight average molecular weight (Mw) of the softening agent (f) is 2000 or less, the softening agent (f) can be prevented from being locally present in the rubber composition and becoming a destruction nucleus. The wear resistance is further improved. The lower limit of the weight average molecular weight (Mw) of the softener (f) is not particularly limited, but is preferably 400 or more.
Here, the weight average molecular weight (Mw) of the softener (f) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  The content of the softener (f) is preferably in the range of 0.1 to 150 parts by mass, more preferably in the range of 1 to 130 parts by mass, and more preferably 5 to 110 parts by mass, per 100 parts by mass of the rubber component (a). The range of parts by mass is even more preferred. When the content of the softener (f) is at least 0.1 part by mass with respect to 100 parts by mass of the rubber component (a), the workability of the rubber composition will be further improved, and at 150 parts by mass or less. If so, the wear resistance of the rubber composition is further improved.

Further, the rubber composition of the present invention preferably contains a silane coupling agent (g) from the viewpoint of increasing the dispersibility of the silica (b1) and further improving the high elastic modulus and the breaking characteristics.
Here, the silane coupling agent (g) is not particularly limited. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercapto Ethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2- Riethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide , 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilyl Propylbenzothiazolyltetrasulfide and the like. These silane coupling agents may be used alone or in a combination of two or more.

  The content of the silane coupling agent (g) is preferably in the range of 3 to 15% by mass (when the content of silica is 100%) with respect to the content of silica, and is preferably 5 to 15% by mass. More preferably, it is in the range of 15 to 15% by mass. When the content of the silane coupling agent is at least 3% by mass with respect to 100 parts by mass of the silica, the effect of improving the high modulus of elasticity and the breaking characteristics of the silica will be sufficiently exhibited, and the content of the silane coupling agent will be reduced. When the content is 15% by mass or less based on 100 parts by mass of silica, gelation of the rubber component (a) can be surely suppressed.

  Further, the rubber composition of the present invention may contain, if necessary, a vulcanization aid, a colorant, a flame retardant, a lubricant, a plasticizer, a processing aid, an antioxidant, an anti-scorch agent, an ultraviolet light inhibitor, and an antistatic agent. Known agents such as agents, color inhibitors, and other compounding agents can be used according to the purpose of use.

<Tire>
The tire of the present invention is characterized by using the rubber composition of the present invention or the rubber composition for a tire described above. By including the rubber composition for a tire or the rubber composition for a tire of the present invention as a tire material, it is possible to achieve both high steering stability and high breaking characteristics.
The site to which the rubber composition or tire rubber composition of the present invention is applied is not particularly limited, but is preferably used for a tread portion. A tire using the rubber composition or the rubber composition for a tire of the present invention in a tread portion can achieve both high steering stability and high breaking characteristics at a high level.
The tire of the present invention is not particularly limited except that the above-described rubber composition for a tire of the present invention is used for any of the tire members, and can be manufactured according to a conventional method. In addition, as the gas to be filled into the tire, there can be used normal gas or air whose oxygen partial pressure is adjusted, or an inert gas such as nitrogen, argon, helium, or the like.

<Rubber articles>
The rubber article of the present invention is characterized by using the rubber composition of the present invention.
The rubber article of the present invention uses a rubber composition capable of achieving both a high level of elasticity after crosslinking and breaking characteristics at a high level, so that excellent durability can be realized.
In addition, there is no restriction | limiting in particular as a kind and manufacturing method of the rubber article of this invention, It can select suitably according to the objective. Here, examples of the rubber article include a vibration-isolating rubber, a seismic isolation rubber, a belt such as a conveyor belt, a rubber crawler, various hoses, and the like. When the rubber composition of the present invention is used for a tire, the application site of the rubber composition is not particularly limited and can be appropriately selected depending on the purpose.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

(Analysis of copolymer)
The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the copolymer synthesized as described below by the following method, butadiene unit, ethylene unit and styrene unit content, The main chain structure was confirmed by measuring the melting point, endothermic peak energy, glass transition temperature, and crystallinity.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT x 2, detector: differential refractometer (RI)] The polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer were determined as standards. The measurement temperature is 40 ° C.

(2) Content of butadiene unit, ethylene unit, and styrene unit The content (mol%) of butadiene unit, ethylene unit, and styrene unit in the copolymer was measured by using a ¹ H-NMR spectrum (100 ° C, d-tetrachloroethane standard). : 6 ppm).

(3) Melting point ( _Tm )
The melting point of the copolymer was measured using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000") in accordance with JIS K 7121-1987.

(4) Endothermic peak energy Using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan Co., Ltd., “DSCQ2000”), the rate of temperature rise at 10 ° C./min according to JIS K 7121-1987. Then, the temperature was raised from -150 ° C. to 150 ° C., and the endothermic peak energy at 0 to 120 ° C. at that time (1st run) was measured.

(5) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the copolymer was measured using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000") in accordance with JIS K 7121-1987.

(6) Crystallinity The crystal melting energy of the 100% crystalline component polyethylene and the melting peak energy of the obtained copolymer were measured, and the crystallinity was calculated from the energy ratio between the polyethylene and the copolymer. The melting peak energy was measured with a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000").

(7) Confirmation of Main Chain Structure The ¹³ C-NMR spectrum of the synthesized copolymer was measured.

(Synthesis method of terpolymer)
160 g of styrene and 600 mL of toluene were added to a sufficiently dried 1000 mL pressure-resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide gadolinium complex {1,3-[(t-Bu) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ] ₂ ｝ 0.25 mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 0.275 mmol, And 1.1 mmol of diisobutylaluminum hydride were charged and dissolved in 40 mL of toluene to prepare a catalyst solution.
The catalyst solution was added to the pressure-resistant stainless steel reactor and heated to 70 ° C.
Next, ethylene was charged into the pressure-resistant stainless steel reactor at a pressure of 1.5 MPa, and 80 mL of a toluene solution containing 20 g of 1,3-butadiene was further charged into the pressure-resistant stainless steel reactor over 8 hours. The copolymerization was performed for 0.5 hours.
Next, 1 ml of a 5% by mass solution of 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in isopropanol was added to the pressure-resistant stainless steel reactor to stop the reaction.
Next, the copolymer was separated using a large amount of methanol, and dried at 50 ° C. under vacuum to obtain a terpolymer.
About the obtained terpolymer, number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), butadiene unit, ethylene unit, styrene unit content, melting point (T _m ), The endothermic peak energy, glass transition temperature (Tg), and crystallinity were measured by the methods described above. The results are shown in Table 1.
When the main chain structure of the obtained terpolymer was confirmed by the above method, no peak was observed at 10 to 24 ppm in the ¹³ C-NMR spectrum chart. It was confirmed that the polymer had a main chain consisting only of an acyclic structure.

<Rubber composition samples 1 to 14>
According to the formulation shown in Table 2, a sample of the rubber composition was prepared using a normal Banbury mixer. The obtained sample was vulcanized at 160 ° C. for 15 minutes to obtain a vulcanized rubber, and the following evaluation was performed. The results are shown in Table 2.

<Evaluation>
(1) Tensile strength (Tb)
For the vulcanized rubber obtained from each sample, the tensile strength Tb (MPa) was measured according to JIS K6251.
The evaluation is shown as an index when the tensile strength Tb of the sample 13 is set to 100, and the larger the index value, the higher the tensile strength and the better the fracture characteristics.

(2) Low loss (tan δ)
Using a spectrometer (manufactured by Kamishima Seisakusho), the loss tangent (tan δ) of the vulcanized rubber obtained from each sample was measured at a temperature of 50 ° C., an initial strain of 0.3%, and a frequency of 10 Hz. .
The evaluation is shown by an index when tan δ of sample 13 is set to 100, and the smaller the index value, the better the low loss property. Table 1 shows the evaluation results.

(3) Shear modulus (G ')
The vulcanized rubber obtained from each sample was measured at a frequency of 10 Hz, a shear strain of 0.3% and a temperature of 50 ° C. using a viscoelasticity measuring device (“ARES-G2” manufactured by TA Instruments). The shear modulus G '(MPa) was measured.
The evaluation is shown as an index value when the shear modulus G ′ of the sample 13 is set to 100, and the larger the index value, the higher the elastic modulus and the more excellent the steering stability.

* 1 Natural rubber: TSR20
* 2 Terpolymer: Ternary copolymer synthesized by the above method * 3 Silica A: Tosoh Silica Co., Ltd., trade name "Nipsil HQ": Please change to CTAB200 in the table.
* 4 Silica B: manufactured by Tosoh Silica Co., Ltd., trade name “Nipsil AQ”
* 5 Silica C: Tosoh Silica Co., Ltd., trade name "Nipsil EQ"
* 6 Silane coupling agent: bistriethoxysilylpropyl polysulfide, manufactured by Shin-Etsu Chemical Co., Ltd. * 7 Process oil: petroleum-based hydrocarbon process oil, manufactured by Idemitsu Kosan Co., Ltd., trade name "DAIANA PROCESS OIL NS-28"
* 8 Wax: Microcrystalline wax, manufactured by Seiko Chemical Co., Ltd. * 9 Anti-aging agent: manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Nocrack 6C"
* 10 Vulcanization accelerator MBTS: di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinko Chemical Co., Ltd., trade name “Noxeller DM-P”
* 11 Vulcanization accelerator NS: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinko Chemical Co., Ltd., trade name “NOXELLER NS-P (NS)”
* 12 Zinc oxide: manufactured by Hakusui Tech Co., Ltd. * 13 Vulcanization accelerator DPG: manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Noxeller D"

  From the results of the examples shown in Table 2, it was found that the rubber compositions of the examples according to the present invention had good evaluation results of tensile strength, low loss property and shear modulus.

ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can make the elastic modulus after bridge | crosslinking and a fracture characteristic compatible at a high level can be provided.
Further, according to the present invention, it is possible to provide a tire in which steering stability and breaking characteristics are compatible at a high level, and a rubber article having excellent durability.

* 1 Natural rubber: TSR20
* 2 Terpolymer: Ternary copolymer synthesized by the above method * 3 Silica A: "Nipsil HQ" manufactured by Tosoh Silica Co., Ltd.
* 4 Silica B: manufactured by Tosoh Silica Co., Ltd., trade name “Nipsil AQ”
* 5 Silica C: Tosoh Silica Co., Ltd., trade name "Nipsil EQ"
* 6 Silane coupling agent: bistriethoxysilylpropyl polysulfide, manufactured by Shin-Etsu Chemical Co., Ltd. * 7 Process oil: petroleum-based hydrocarbon process oil, manufactured by Idemitsu Kosan Co., Ltd., trade name "DAIANA PROCESS OIL NS-28"
* 8 Wax: Microcrystalline wax, manufactured by Seiko Chemical Co., Ltd. * 9 Anti-aging agent: manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Nocrack 6C"
* 10 Vulcanization accelerator MBTS: di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinko Chemical Co., Ltd., trade name “Noxeller DM-P”
* 11 Vulcanization accelerator NS: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinko Chemical Co., Ltd., trade name “NOXELLER NS-P (NS)”
* 12 Zinc oxide: manufactured by Hakusui Tech Co., Ltd. * 13 Vulcanization accelerator DPG: manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Noxeller D"

Claims (16)

A rubber component containing a multicomponent copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit,
30 to 70 parts by mass of silica with respect to 100 parts by mass of the rubber component,
The silica composition, wherein the silica has a CTAB adsorption specific surface area of 170 m ² / g or more. The silica is characterized by a BET specific surface area of 200 meters ² / g or more, the rubber composition according to claim 1. The rubber composition according to claim 1, wherein the silica has a CTAB adsorption specific surface area of 190 m ² / g or more.   The rubber composition according to any one of claims 1 to 3, further comprising 3 to 15% by mass of a silane coupling agent based on the content of the silica.   The rubber composition according to any one of claims 1 to 4, wherein the content of the multicomponent copolymer in the rubber component is 70% by mass or more.   In the multi-component copolymer, the content of the conjugated diene unit is 1 to 50 mol%, the content of the non-conjugated olefin unit is 40 to 97 mol%, and the content of the aromatic vinyl unit is 2 to 35 mol. %, And the rubber composition according to any one of claims 1 to 5.   The multi-component copolymer according to any one of claims 1 to 6, wherein an endothermic peak energy measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C is 10 to 150 J / g. The rubber composition as described in the above.   The rubber composition according to any one of claims 1 to 7, wherein the melting point of the multicomponent copolymer measured by a differential scanning calorimeter (DSC) is 30 to 130 ° C.   The rubber composition according to any one of claims 1 to 8, wherein the multi-component copolymer has a glass transition temperature of 0 ° C or lower measured by a differential scanning calorimeter (DSC).   The rubber composition according to any one of claims 1 to 9, wherein the multi-component copolymer has a crystallinity of 0.5 to 50%.   The rubber composition according to any one of claims 1 to 10, wherein in the multicomponent copolymer, the non-conjugated olefin unit is a non-cyclic non-conjugated olefin unit.   The rubber composition according to claim 11, wherein the non-cyclic non-conjugated olefin unit of the multi-component copolymer comprises only ethylene units.   The rubber composition according to any one of claims 1 to 12, wherein in the multi-component copolymer, the aromatic vinyl unit includes a styrene unit.   The rubber composition according to any one of claims 1 to 13, wherein in the multicomponent copolymer, the conjugated diene unit includes a 1,3-butadiene unit and / or an isoprene unit.   A tire using the rubber composition according to any one of claims 1 to 14.   A rubber article using the rubber composition according to any one of claims 1 to 14.