WO2019216109A1

WO2019216109A1 - Vulcanized rubber composition, tire tread and tire

Info

Publication number: WO2019216109A1
Application number: PCT/JP2019/015827
Authority: WO
Inventors: 靖宏庄田; 茂樹大石
Original assignee: 株式会社ブリヂストン
Priority date: 2018-05-08
Filing date: 2019-04-11
Publication date: 2019-11-14
Also published as: JPWO2019216109A1

Abstract

The purpose of the present invention is to provide a rubber composition having excellent wear resistance and workability.　In order to achieve the foregoing, the vulcanized rubber composition according to the present invention comprises a rubber component that includes a multicomponent copolymer containing a conjugated diene unit, a non-conjugated olefin unit and an aromatic vinyl unit, and said vulcanized rubber composition is characterized by having a surface roughness of 5 to 100 μm.

Description

Vulcanized rubber composition, tire tread and tire

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

Conventionally, studless tires with softened tread rubber have been used as tires for safe driving on ice in addition to normal road surfaces. By softening the tread rubber, the on-ice performance of the tire can be improved. Are known. However, in general, a tire including a soft tread rubber has a problem of poor wear resistance on a normal road surface, and the on-ice performance and the wear resistance of the tire are in a trade-off relationship.

In addition, as a technique for improving the on-ice performance of the tire, a technique for improving the on-ice performance of the tire by blending organic fiber, glass fiber or the like with the rubber composition used for the tread and scratching the icy road surface is known. ing. However, when the above-mentioned organic fiber or glass fiber is included in the rubber composition, it does not interact with the rubber and thus acts as a fracture nucleus, which causes a decrease in the fracture resistance (abrasion resistance) of the tread rubber. .
Therefore, as a rubber composition for a tire that solves such a problem, for example, Patent Document 1 discloses that 0.5 to 20 parts by weight of potassium titanate fiber is used with respect to 100 parts by weight of a rubber component made of natural rubber and butadiene rubber. And a rubber composition containing 5 to 200 parts by weight of carbon black having an iodine adsorption amount of 100 to 300 mg / g, which is a tread having a two-layer structure comprising a cap tread and a base tread. It is known that the performance on ice (performance on ice and snow) is improved while suppressing a decrease in wear resistance.

JP 2008-303334 A

However, in the technique of Patent Document 1, although the effect of improving the performance on ice (coefficient of friction on ice) of the tire can be expected by blending a specific amount of potassium titanate fiber (see Table 1 of Patent Document 1), the anti-resistance. Abrasion tends to be slightly reduced, and it has been difficult to achieve both high performance on ice and wear resistance.

Accordingly, an object of the present invention is to provide a vulcanized rubber composition that solves the above-described problems of the prior art and can achieve both high performance on ice and wear resistance of a tire.
Moreover, an object of this invention is to provide the tire tread and tire which are excellent in both on-ice performance and abrasion resistance.

The gist configuration of the present invention for solving the above problems is as follows.
The vulcanized rubber composition of the present invention is a vulcanized rubber composition, wherein the rubber component comprises a multi-component copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, The surface roughness of the vulcanized rubber composition is 5 to 100 μm.
By providing the above configuration, when the vulcanized rubber composition of the present invention is used for a tire, both on-ice performance and wear resistance can be achieved at a high level.

In the vulcanized rubber composition of the present invention, the vulcanized rubber composition preferably has a plurality of voids and a porosity of 10 to 80%. In this case, the on-ice performance and wear resistance of the vulcanized rubber composition can be achieved at a higher level.

In the vulcanized rubber composition of the present invention, the multi-component 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 The group vinyl unit content is preferably 2 to 35 mol%. In this case, the wear resistance and weather resistance of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, the multi-component copolymer preferably has a melting point of 30 to 130 ° C. measured with a differential scanning calorimeter (DSC). In this case, the on-ice performance and abrasion resistance of the vulcanized rubber composition can be further improved.

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

In the vulcanized rubber composition of the present invention, the multi-component copolymer preferably has a glass transition temperature of 0 ° C. or less as measured by a differential scanning calorimeter (DSC). In this case, the performance on ice of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, the multi-component copolymer preferably has a crystallinity of 0.5 to 50%. In this case, the on-ice performance and abrasion resistance of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, the multi-component copolymer is preferably such that the non-conjugated olefin unit is an acyclic non-conjugated olefin unit, and the non-cyclic non-conjugated olefin unit is composed only of ethylene units. More preferably. In this case, the weather resistance of the vulcanized rubber composition can be improved.

In the vulcanized rubber composition of the present invention, it is preferable that in the multi-component copolymer, the aromatic vinyl unit includes a styrene unit. In this case, the weather resistance of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, it is preferable that in the multicomponent copolymer, the conjugated diene unit includes a 1,3-butadiene unit and / or an isoprene unit. In this case, the wear resistance of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, the content of the multi-component copolymer in the rubber component is preferably 5 to 100% by mass. In this case, the on-ice performance and abrasion resistance of the vulcanized rubber composition can be further improved.

In the vulcanized rubber composition of the present invention, the vulcanized rubber composition preferably further contains a void introducing agent, and the void introducing agent is a foaming agent, a hydrophilic short fiber, a metal sulfate salt, a thermally expandable microcapsule. And at least one selected from the group consisting of porous cellulose particles. In this case, the performance on ice of the vulcanized rubber composition can be further improved.

The tire tread of the present invention is characterized by using the above vulcanized rubber composition.
By providing the above configuration, the tire tread of the present invention is excellent in both on-ice performance and wear resistance.

Furthermore, a tire according to the present invention includes the above-described tire tread.
By providing the above configuration, the tire of the present invention is excellent in both on-ice performance and wear resistance.

ADVANTAGE OF THE INVENTION According to this invention, the vulcanized rubber composition which can make the performance on ice and abrasion resistance of a tire compatible on a high level can be provided.
Moreover, according to this invention, the tire tread and tire which are excellent in both on-ice performance and abrasion resistance can be provided.

It is the figure which showed typically the state of the surface about one Embodiment of the vulcanized rubber composition of this invention.

Hereinafter, an embodiment of a vulcanized rubber composition, a tire tread, and a tire according to the present invention will be described with reference to the drawings as necessary.

<Vulcanized rubber composition>
The vulcanized rubber composition of the present invention is a vulcanized rubber composition comprising a multi-component copolymer in which the rubber component contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, The surface roughness of the vulcanized rubber composition is 5 to 100 μm.

As for the multi-component copolymer contained as a rubber component of the vulcanized rubber composition of the present invention, as one of its characteristics, microcrystals in which non-conjugated olefin units are chained in the molecule collapse under high strain. There is energy dissipation due to melting energy. In addition, since the vulcanized rubber composition has surface roughness (unevenness), water generated from melted ice can be taken into the recesses on the surface and escaped, and a scratching effect due to surface unevenness can be obtained. The improvement on ice performance can be expected.
The vulcanized rubber composition of the present invention includes the above-described multi-component copolymer and has a specific surface roughness (unevenness) of 5 to 100 μm, thereby improving the performance on ice when applied to a tire. In addition to being able to perform, since the surface is locally subjected to a large strain, the above-mentioned energy dissipation due to the melting energy can be effectively exhibited. As a result, in addition to being able to disperse the friction energy when the vulcanized rubber composition of the present invention is used as a tire, the contact area between the tire and the ice surface can be increased, so that the performance on ice and the wear resistance are high. It becomes possible to achieve both levels.

The surface roughness (Ra) of the vulcanized rubber composition of the present invention is required to be 5 to 100 μm. When the surface roughness is less than 5 μm, the unevenness of the surface is too small, so performance on ice cannot be obtained when used in a tire, and the energy dissipation effect due to melting energy is also small, so that sufficient resistance Abrasion is not obtained. From the same viewpoint, the surface roughness is preferably 10 μm or more, and more preferably 15 μm or more. On the other hand, if the surface roughness exceeds 100 μm, sufficient wear resistance cannot be obtained. From the same viewpoint, the surface roughness is preferably 90 μm or less, more preferably 80 μm or less, further preferably 70 μm or less, and particularly preferably 60 μm or less.
The surface roughness (Ra) of the vulcanized rubber composition of the present invention is measured according to JIS B 0601 (2001).

Although the vulcanized rubber composition of the present invention has a specific surface roughness, the method for adjusting the surface roughness is not particularly limited, and conditions for surface roughness and the vulcanized rubber composition A known technique can be used depending on the equipment to be manufactured.
For example, the method of giving roughness by shaving the surface of a vulcanized rubber composition with a grinder, sputtering, etc. is mentioned. Further, as described later, in the rubber composition before vulcanization, by blending a void-introducing agent such as a foaming agent, hydrophilic short fiber, sulfate metal salt, thermally expandable microcapsule, porous cellulose particles, Examples thereof include a method in which voids are provided in the vulcanized rubber composition and irregularities are formed on the surface.

Among the above-described methods, a void-introducing agent is included in the rubber composition before vulcanization from the viewpoint that the surface roughness (Ra) of the vulcanized rubber composition can be reliably kept in the range of 5 to 100 μm. Is preferable.
Here, FIG. 1 schematically shows the state of the surface when the void 20 is provided in the vulcanized rubber composition 10 of the present invention. As shown in FIG. 2, a predetermined surface roughness can be formed on the surface of the vulcanized rubber composition because the voids of the voids 20 exposed on the surface become concave portions.

The porosity of the vulcanized rubber composition of the present invention is preferably 10 to 80%. By setting the lower limit of the porosity to 10%, it is possible to improve the performance on ice and the wear resistance more reliably. From the same viewpoint, the porosity is preferably 15% or more, and more preferably 20% or more. On the other hand, by setting the upper limit value of the porosity to 80%, it is possible to more reliably suppress a decrease in wear resistance even when a plurality of voids are provided. From the same viewpoint, the porosity is preferably 60% or less, and more preferably 40% or less.
The porosity is a volume ratio (volume%) of the voids in the vulcanized rubber composition of the present invention. The method for measuring the porosity is not particularly limited, and for example, it can be measured using a hydrometer (ViBRA hydrometer “DMA-220” manufactured by Shinko Denshi Co., Ltd.).

The vulcanized rubber composition is a vulcanized rubber obtained by vulcanizing an unvulcanized rubber composition. Further, the vulcanization conditions (temperature, time) are not particularly limited, and the vulcanization treatment can be performed under arbitrary conditions according to the required performance.
The unvulcanized rubber composition (hereinafter sometimes simply referred to as “rubber composition”), which is the basis of the vulcanized rubber composition of the present invention, will be described below.

The rubber composition includes a rubber component (a), and the rubber component (a) includes a multi-component copolymer (a1) containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. Including.
Here, the multi-component copolymer (a1) contains at least a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and includes a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. It may consist of only, and can also contain another monomer unit.

The conjugated diene unit is a structural unit derived from a conjugated diene compound as a monomer. The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compound may be a single kind or a combination of two or more kinds. And the conjugated diene compound as a monomer of the multi-component copolymer is 1, 3 from the viewpoint of effectively improving the wear resistance of a vulcanized rubber composition or a tire using the obtained multi-component copolymer. -It preferably contains butadiene and / or isoprene, more preferably consists only of 1,3-butadiene and / or isoprene, and more preferably consists only of 1,3-butadiene. In other words, the conjugated diene unit in the multi-component copolymer preferably contains 1,3-butadiene units and / or isoprene units, and more preferably consists only of 1,3-butadiene units and / or isoprene units. Preferably, it consists of only 1,3-butadiene units.

In the multi-component 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, % Or less, more preferably 30 mol% or less, even more preferably 25 mol% or less, and even more preferably 15 mol% or less. When the content of the conjugated diene unit is 1 mol% or more of the whole multi-component copolymer, a vulcanized rubber composition and a rubber product excellent in elongation can be obtained, and when it is 50 mol% or less, weather resistance is excellent. In addition, 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%, based on the whole multi-component copolymer.

The non-conjugated olefin unit is a structural unit derived from a non-conjugated olefin compound as a monomer. The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of such non-conjugated olefin compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and other α-olefins, vinyl pivalate, 1-phenylthioethene. And heteroatom-substituted alkene compounds such as N-vinylpyrrolidone. The non-conjugated olefin compound may be a single kind or a combination of two or more kinds. The non-conjugated olefin compound as a monomer of the multi-component copolymer further reduces the crystallinity of the resulting multi-component copolymer, and weather resistance of vulcanized rubber compositions and tires using such a multi-component copolymer. From the viewpoint of further improving the properties, it is preferably an acyclic non-conjugated olefin compound, and the acyclic non-conjugated olefin compound is more preferably an α-olefin, which is an α-olefin containing ethylene. More preferably, it is particularly preferable that it consists only of ethylene. In other words, the non-conjugated olefin unit in the multi-component copolymer is preferably an acyclic non-conjugated olefin unit, and the acyclic non-conjugated olefin unit is preferably an α-olefin unit. More preferably, it is more preferably an α-olefin unit containing an ethylene unit, and further preferably only an ethylene unit.

In the multi-component copolymer (a1), the content of the non-conjugated olefin unit is preferably 40 mol% or more, more preferably 45 mol% or more, and even more preferably 55 mol% or more, It is particularly preferably 60 mol% or more, more preferably 97 mol% or less, still more preferably 95 mol% or less, and even more preferably 90 mol% or less. When the content of the non-conjugated olefin unit is 40 mol% or more of the entire multi-polymer, the content of the conjugated diene unit or the aromatic vinyl unit is decreased as a result, and the weather resistance is improved or the resistance at room temperature is increased. Breakability (particularly, breaking strength (Tb)) is 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 fracture resistance at high temperature (particularly, elongation at break (Eb)) Will improve. Further, 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% with respect to the entire multi-component copolymer.

The aromatic vinyl unit is a structural unit derived from an aromatic vinyl compound as a monomer. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Examples of 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 a single type or a combination of two or more types. The aromatic vinyl compound as a monomer of the multi-component copolymer further reduces the crystallinity of the resulting multi-component copolymer, and weather resistance of vulcanized rubber compositions and tires using such a multi-component copolymer. From the viewpoint of further improving the properties, it is preferable that styrene is included, and it is more preferable that the styrene only be included. In other words, the aromatic vinyl unit in the multi-component copolymer preferably includes a styrene unit, and more preferably includes only a styrene unit.
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 multi-component copolymer (a1), the content of the aromatic vinyl unit is preferably 2 mol% or more, more preferably 3 mol% or more, and preferably 35 mol% or less, More preferably, it is 30 mol% or less, and further more preferably 25 mol% or less. When the content of the aromatic vinyl unit is 2 mol% or more, the fracture resistance at high temperatures is improved. Moreover, the effect by a conjugated diene unit and a nonconjugated olefin unit becomes remarkable as content of an aromatic vinyl unit is 35 mol% or less. 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%, still more preferably in the range of 3 to 25 mol% with respect to the entire multi-component copolymer.

The number of types of monomers of the multi-component copolymer (a1) is not particularly limited as long as the multi-component copolymer contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. The multi-component copolymer (a1) may have other structural units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit, but the content of the other structural unit is desired. From the viewpoint of obtaining the effect of the above, it is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and not contained, that is, the content of the entire multi-component copolymer. Is particularly preferably 0 mol%.

The multi-component copolymer (a1) has a kind of conjugated diene compound, a kind of non-conjugated olefin compound, and a kind of aromatic as a monomer from the viewpoint of preferable wear resistance, weather resistance and crystallinity. A polymer obtained by polymerization using at least a vinyl compound is preferable. 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. More preferably, it is a terpolymer comprising only a conjugated diene unit, a non-conjugated olefin unit, and a single aromatic vinyl unit, and is composed only of a 1,3-butadiene unit, an ethylene unit, and a styrene unit. More preferably, it is a terpolymer. Here, the “one type of conjugated diene unit” includes conjugated diene units having different bonding modes.

Furthermore, the multi-component 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 a content of the aromatic vinyl unit. The amount is preferably 2 to 35 mol%. In this case, the abrasion resistance of the vulcanized rubber composition is further improved, and the weather resistance is also improved.

The multi-component copolymer (a1) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000, more preferably 100,000 to 9,000,000. 150,000 to 8,000,000 is more preferable. When the Mw of the multi-component copolymer is 10,000 or more, the mechanical strength of the vulcanized rubber composition can be sufficiently secured, and the Mw is 10,000,000 or less. High workability 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. More preferably, it is 100,000 to 8,000,000. When the Mn of the multi-component copolymer is 10,000 or more, the mechanical strength of the vulcanized rubber composition can be sufficiently secured, and the Mn is 10,000,000 or less. High workability can be maintained.

The multi-component copolymer (a1) preferably has a molecular weight distribution [Mw / Mn (weight average molecular weight / number average molecular weight)] of 1.00 to 4.00, preferably 1.50 to 3.50. Is more preferable, and is more preferably 1.80 to 3.00. If the molecular weight distribution of the multi-component copolymer is 4.00 or less, sufficient homogeneity can be brought about in the physical properties of the multi-component copolymer.

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.

The multi-component copolymer (a1) preferably has a melting point measured by a differential scanning calorimeter (DSC) of 30 to 130 ° C., more preferably 30 to 110 ° C. If the melting point of the multi-component copolymer (a1) is 30 ° C. or higher, the crystallinity of the multi-component copolymer (a1) is increased, the wear resistance of the vulcanized rubber composition is further improved, and 130 ° C. or lower. If so, the performance on ice is further improved.
Here, the said melting | fusing point is the value measured by the method as described in an Example.

Further, the multi-component copolymer (a1) preferably has an endothermic peak energy measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. of 10 to 150 J / g, preferably 30 to 120 J / g. Is more preferable. If 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, and the wear resistance of the vulcanized rubber composition is further improved. If it is 150 J / g or less, the performance on ice will further improve.
Here, the endothermic peak energy is a value measured by the method described in Examples.

The multi-component copolymer (a1) preferably has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 0 ° C. or lower, more preferably −100 to −10 ° C. . When the glass transition temperature of the multi-component copolymer (A1) is 0 ° C. or lower, the performance on ice of the vulcanized rubber composition is further improved.
Here, the said glass transition temperature is the value measured by the method as described in an Example.

Furthermore, the multi-component copolymer (a1) preferably has a crystallinity of 0.5 to 50%, more preferably 3 to 45%, and even more preferably 5 to 45%. . When the degree of crystallinity of the multi-component copolymer (a1) is 0.5% or more, sufficient crystallinity due to the non-conjugated olefin unit is secured, and the wear resistance of the vulcanized rubber composition is further improved. . Moreover, if the crystallinity of the multi-component copolymer (a1) is 50% or less, the workability during kneading of the rubber composition is improved, and the performance on ice of the vulcanized rubber composition is also improved.
Here, the crystallinity is a value measured by the method described in Examples.

Furthermore, the multi-component copolymer (a1) preferably has a main chain consisting only of an acyclic structure. This is because the wear resistance can be further improved. Incidentally, NMR is used as a main measuring means for confirming whether or not the main chain of the copolymer 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 ring to a five-membered ring) is not observed, the main chain of the copolymer is It shows that it consists only of an acyclic structure.

The multi-component copolymer (a1) can be produced through a polymerization process using a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound as monomers, and, if necessary, a coupling process. , A cleaning process, and other processes may be performed.
Here, in the production of the multi-component copolymer (a1), it is preferable to add only a non-conjugated olefin compound and an aromatic vinyl compound without adding a conjugated diene compound and polymerize them in the presence of a catalyst. . In particular, when the polymerization catalyst composition described later is used, the reactivity of the conjugated diene compound is higher than that of the non-conjugated olefin compound and the aromatic vinyl compound, so that the non-conjugated olefin compound and / or the aromatic compound is present in the presence of the conjugated diene compound. It is difficult to polymerize the group vinyl compound. In addition, it is easy to polymerize the conjugated diene compound first, and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound later due to the characteristics of the catalyst.

As the 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. In addition, when a solvent is used for the polymerization reaction, such a solvent is not particularly limited as long as it is inert in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

The polymerization process may be performed in one stage, or may be performed in two or more stages. The one-step polymerization process means 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 polymerized by reacting simultaneously. The multi-stage polymerization process means that a polymer is formed by first reacting part or all of one or two kinds of monomers (first polymerization stage), and then the remaining kinds of monomers. Or a step of polymerizing by performing one or more stages (second polymerization stage to final polymerization stage) in which the remainder of the one or two kinds of monomers is added and polymerized. In particular, in the production of multi-component copolymers, it is preferable to carry out the polymerization process in multiple stages.

In the polymerization step, the polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. The pressure for 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. Also, the reaction time of the above polymerization reaction is not particularly limited and is preferably in the range of, for example, 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 polymerization step of the conjugated diene compound, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.

The polymerization process is preferably performed in multiple stages. More preferably, a first step of obtaining a polymerization mixture by mixing a first monomer raw material containing at least an aromatic vinyl compound and a polymerization catalyst, and a conjugated diene compound, a non-conjugated olefin compound, and It is preferable to carry out the second step of introducing the second monomer raw material containing at least one selected from the group consisting of aromatic vinyl compounds. Furthermore, it is more preferable that the first monomer raw material does not contain a conjugated diene compound, and the second monomer raw 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. Moreover, the 1st monomer raw material may contain the whole quantity of the aromatic vinyl compound to be used, and may contain only one part. The non-conjugated olefin compound is contained in at least one of the first monomer raw material and the second monomer raw material.

The first step is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas, in the reactor. The temperature (reaction temperature) in the first step is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can 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 incorporate the aromatic vinyl compound into the polymerization reaction system. The time spent in the first step (reaction time) 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 ˜500 minutes is preferred.

In the first step, the polymerization method for obtaining the polymerization mixture may be 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. Further, when a solvent is used for the polymerization reaction, such a solvent may be any inactive in the polymerization reaction, and examples thereof include toluene, cyclohexanone, normal hexane and the like.

The second monomer raw material used in the second step is a conjugated diene compound only, 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. It is preferable that they are a compound and an aromatic vinyl compound.
In addition, when the second monomer raw material includes 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 raw materials are preliminarily used as a solvent or the like. After mixing together, it may be introduced into the polymerization mixture, or each monomer raw material may be introduced from a single state. Moreover, each monomer raw material may be added simultaneously, and may be added sequentially. In the second step, the method for introducing the second monomer raw material into the polymerization mixture is not particularly limited, but it is continuously added to the polymerization mixture by controlling the flow rate of each monomer raw material. It is preferable to perform (so-called metering). Here, when a monomer raw material that is a gas under the conditions of the polymerization reaction system (for example, ethylene as a non-conjugated olefin compound under the conditions of room temperature and atmospheric pressure) is used, the polymerization reaction system is used at a predetermined pressure. Can be introduced.

The second step is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas, in the reactor. The temperature (reaction temperature) in the second step is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. When the reaction temperature is raised, the selectivity of cis-1,4 bond in the conjugated diene unit may be lowered. 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 monomers such as a conjugated diene compound into the polymerization reaction system. The time spent in the second step (reaction time) can be appropriately selected depending on conditions such as the type of polymerization catalyst and reaction temperature, but is preferably in the range of 0.1 hour to 10 days, for example.
In the second step, the polymerization reaction may be stopped using a polymerization terminator such as methanol, ethanol, or isopropanol.

Here, the polymerization step of the non-conjugated olefin compound, aromatic vinyl compound, and conjugated diene compound preferably includes a step of polymerizing various monomers in the presence of the catalyst component described below.
Examples of the catalyst component include components (A) to (F). One or more of each component can be used, and a combination of two or more of the following components (A) to (F) More preferably, it is used as a product.
(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 ( F) Component: substituted or unsubstituted cyclopentadiene (compound having a cyclopentadienyl group), substituted or unsubstituted indene (compound having an indenyl group), and substituted or unsubstituted fluorene (compound having a fluorenyl group) ) -Containing cyclopentadiene skeleton-containing compound (hereinafter, simply referred to as “cyclopentadiene skeleton-containing compound”)

Hereinafter, 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 having a rare earth element-carbon bond, or a reaction product of the rare earth element compound and a Lewis base (hereinafter referred to as a rare earth element compound). , Also referred to as “component (A-1)”), 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 referred to as “component (A-2)”) Say).

(A-1) The rare earth element compound or reactant having a rare earth element-carbon bond 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 an unsubstituted or substituted indenyl group, and R ^a to R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A metallocene complex represented by the following formula (II): and a group or a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3.

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an 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, and w represents an integer of 0 to 3, and a metallocene complex represented by Formula (III):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxy group or 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 non- At least one complex selected from the group consisting of half metallocene cation complexes represented by

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-x R _x or C ₉ H _11-x R _x . Here, X is an integer of 0 to 7 or 0 to 11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 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 the metalloid of the metalloid group include germyl Ge, stannyl Sn, silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is It is the same. 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 ^Rs 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 above general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that

In the general formula (III), Cp ^{R ′} having the cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-x R _x . Here, X is an integer of 0 to 5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 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 the metalloid of the metalloid group include germyl Ge, stannyl Sn, silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is It is the same. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

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

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

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-x R _x or C ₁₃ H _17-x R _x . Here, X is an integer of 0 to 9 or 0 to 17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 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 the metalloid of the metalloid group include germyl Ge, stannyl Sn, silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is It is the same. 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 of 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^a to R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. In addition, at least one of R ^a to R ^f is preferably a hydrogen atom. By making at least one of R ^a to R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk around silicon is reduced, so that non-conjugated olefin compounds and aromatic vinyl compounds are introduced. It becomes easy. 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, the alkyl group is preferably a methyl group.

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 or an iodine atom, but is preferably a chlorine atom or a bromine atom.

In the general formula (III), the alkoxy group represented by X is 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, or a tert-butoxy group; a 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 Examples include aryloxy groups such as -neopentylphenoxy group and 2-isopropyl-6-neopentylphenoxy group. Among these, 2,6-di-tert-butylphenoxy group is preferable.

In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.
In the general formula (III), the amino group represented by X is an aliphatic amino group such as a dimethylamino group, a diethylamino group or 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- Examples thereof include arylamino groups such as 6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group. Among these, bistrimethylsilylamino Groups are preferred.

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

In the general formula (III), as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by X, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group , Sec-butyl group, tert-butyl group, neopentyl group, hexyl group, octyl group and other linear or branched aliphatic hydrocarbon groups; phenyl group, tolyl group, naphthyl group and other aromatic hydrocarbon groups; In addition to aralkyl groups such as benzyl groups; hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl groups and bistrimethylsilylmethyl groups, etc., among these, methyl groups, ethyl groups, isobutyl groups, trimethylsilylmethyl groups, etc. Is preferred. In 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. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarboundeborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

The metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) may further have 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 includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.
In addition, the metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, or a dimer. Or it may exist as a multimer more than that.

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

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

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

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

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 is An integer from 0 to 3 is shown. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. The ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol based on the metallocene complex. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or compounds of the general formula represented by the general formula (IV) used in the reaction [a] + ^[B] ^- provides separately into the polymerization reaction system an ionic compound represented by the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (I) or (II) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A 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.
Furthermore, as another (A-1) component,
The following general formula (V):
R _a MX _b QY _b (V)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents carbon. 1 represents a monovalent hydrocarbon group of 1 to 20, wherein X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y represents each independently a carbon number 1 to 20 monovalent hydrocarbon groups or hydrogen atoms, wherein Y is coordinated to Q, and a and b are 2).

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

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently represents a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
By using the metallocene polymerization catalyst, a multi-component copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used during the synthesis of the multi-component copolymer. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of synthesizing the multi-component copolymer. For example, in the conventional catalyst system, it is necessary to use an alkylaluminum of 10 molar equivalents or more with respect to the metal catalyst. However, in the case of the metallocene composite catalyst, it is excellent by adding about 5 molar equivalents of alkylaluminum. Catalysis is exerted.

In the metallocene 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 of 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

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

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

In the above 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 methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group. Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the general formula (V), each 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 methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group. Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

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

In the general formula (VI), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7X R _X or C ₉ H _11X R _X. Here, X is an integer of 0 to 7 or 0 to 11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 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 the metalloid of the metalloid group include germyl Ge, stannyl Sn, silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is It is the same. Specific examples of the metalloid group include a trimethylsilyl group.
Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. Incidentally, the two Cp ^R in the formula (VI) may each be the same or different from each other.

In the general formula (VI), R ^A and R ^B each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M ¹ and Al. is 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 group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group 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 group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

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

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

In the metallocene complex represented by the 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 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 formula (VI).

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

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 includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

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

On the other hand, the organoaluminum compound used to produce the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. hydrogen group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that, R ^M may be the same or different and the R ^K or R ^L. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, 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, tri Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. The amount of the organoaluminum compound used for producing the metallocene composite catalyst is preferably 1 to 50 times mol, more preferably about 10 times mol to the metallocene complex.

(A-2) The rare earth element compound or reaction product having no rare earth element-carbon bond (A-2) The component is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, where The rare earth element compound and the reaction product of the rare earth element compound and the Lewis base do not have a 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 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 rare earth metal divalent or trivalent salt or complex compound, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (VIII) or (IX):
M ¹¹ X ¹¹ ₂ · L ¹¹ _w (VIII)
M ¹¹ X ¹¹ ₃ · L ¹¹ _w (IX)
(In each formula, M11 is a lanthanoid element, scandium or yttrium, X ¹¹ are each independently a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group, an aldehyde residue, ketone A 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) bonded to the rare earth element of the rare earth element compound include a hydrogen atom, a halogen atom, an alkoxy group (a group in which an alcohol hydroxyl group is removed, and forms a metal alkoxide), a thiolate group ( A group obtained by removing hydrogen from a thiol group of a thiol compound and forming 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) And forms a metal amide), silyl group, aldehyde residue, ketone residue, carboxylic acid residue, thiocarboxylic acid residue, and 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, thio n-butoxy group, thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy Aliphatic thiolate groups such as thiophene groups; thiophenoxy groups, 2,6-di-tert-butyl Ofenoxy 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, 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; trimethylsilyl group, tris (trimethylsilyl) Silyl groups such as silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. .
As the group (ligand), a residue of an aldehyde such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone Residues of hydroxyphenone such as 2′-hydroxypropiophenone; Ketone residues (especially diketone residues) such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, 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 chemistry ( Made by 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, succinic acid; hexanethioic acid, 2,2- Residues of thiocarboxylic acids such as dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, 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) ) Residues of phosphate esters such as (p-nonylphenyl); 2-ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphonate mono-2-ethylhexyl, 2-ethylhexylphosphonate mono- residues of phosphonates 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-Mech Ruheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p- Mention may also be made of phosphinic acid residues such as nonylphenylphosphinic acid.
In addition, these groups (ligand) may be used individually by 1 type, and may be used in combination of 2 or more type.

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, when the rare earth element compound reacts with a plurality of Lewis bases (when w is 2 or 3 in the general formulas (VIII) and (IX)), the Lewis base L ¹¹ may be the same. 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; provided that it has 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, and 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 catalyst activity and 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 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, 2-isopropyl-6-neopentylphenylamino group, Examples include arylamino groups such as 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group, and are particularly soluble in aliphatic hydrocarbons and aromatic hydrocarbons. From the viewpoint, a bistrimethylsilylamino group is preferable. The said amino group may be used individually by 1 type, and may be used in combination of 2 or more type.
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. Become.
Moreover, if it is set as the said structure, the catalyst activity in a reaction system can further be 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. For example, the following general formula (XI):
(RO) ₃ M (XI)
Or a rare earth alcoholate represented by the following general formula (XII):
(R-CO ₂ ) ₃ M (XII)
And rare earth carboxylates represented by Here, in the general formulas (XI) and (XII), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.
As the component (A-2), the compound (XI) or the compound (XII) described above can be preferably used because it preferably has no bond between rare earth elements and carbon.

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. For example, the following general formula (XIII):
(RS) ₃ M (XIII)
Or a rare earth alkylthiolate represented by the following general formula (XIV):
(R-CS ₂ ) ₃ M (XIV))
And the like. Here, in the general formulas (XIII) and (XIV), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.

In addition, as the component (A-2), since it is preferable not to have a bond between a rare earth element and carbon, the above-described compound (XIII) or compound (XIV) can be suitably used.

(B) Organometallic compound About the said (B) component, following general formula (XV):
YR ¹ _a R ² _b R ³ _c (XV)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are monovalent hydrocarbons having 1 to 10 carbon atoms. R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is a periodic rule When it is a metal selected from group 1 of the table, a is 1 and b and c are 0, and when Y is a metal selected from groups 2 and 12 of the periodic table , A and b are 1 and c is 0, and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table) And the following general formula (XVI):
AlR ¹ R ² R ³ (XVI)
(In the formula, R ¹ and R ² are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms, R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² and R ³ may be the same or different from each other).

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, dihydrogen hydride Isohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propiyl Aluminum dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred.

The component (B) can be used singly or in combination of two or more. In addition, when the component (B) is used together with the component (A), the amount is preferably 1 to 50 times mol, more preferably about 10 times mol to the component (A). preferable.

(C) Aluminoxane The component (C) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other.
By using the component (C), the catalytic activity in the polymerization reaction system can be further improved. Therefore, the reaction time can be further shortened and the reaction temperature can be further increased.

Here, examples of the organoaluminum compound include trialkylaluminum 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.

Examples of the component (C) include 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 And 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 formula (XVII) is preferably 10 or more.
In addition, regarding R ⁷ in the above formula (XVII), examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, and the like, and a methyl group is particularly preferable. The hydrocarbon group may be one kind or a combination of two or more kinds. Regarding R ⁷ in 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 marketed as a hexane solution is preferable.
Here, examples of the aliphatic hydrocarbon include hexane and cyclohexane.

The component (C) is particularly represented by the following formula (XVIII):
-(Al (CH ₃ ) _x (iC ₄ H ₉ ) _y O) _m- (XVIII)
(Wherein, x + y is 1; m is 5 or more), and may be a modified aluminoxane (hereinafter also referred to as “TMAO”). An example of TMAO is a product name “TMAO341” manufactured by Tosoh Fine Chemical Co., Ltd.

In addition, the component (C) is particularly represented by the following formula (XIX):
-(Al (CH ₃ ) _0.7 (iC ₄ H ₉ ) _0.3 O) _k- (XIX) (wherein k is 5 or more) , Also referred to as “MMAO”). An example of MMAO is a product name “MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.

Furthermore, the component (C) is particularly represented by the following formula (XX):
-[(CH ₃ ) AlO] _i- (XX)
(Wherein i is 5 or more), a modified aluminoxane (hereinafter also referred to as “PMAO”). An example of PMAO is a product name “TMAO-211” manufactured by Tosoh Fine Chemical Co., Ltd.

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

The component (C) can be used singly or in combination of two or more. Further, from the viewpoint of improving the catalytic activity, the component (C), when used together with the component (A), is 10 mol of aluminum in the component (C) with respect to 1 mol of the rare earth element in the component (A). It is preferably used so as to be above, more preferably used so as to be 100 mol or more, and preferably used so as to be 1000 mol or less, and used so as to be 800 mol or less. More preferably.

(D) Ionic compound The component (D) comprises a non-coordinating anion and a cation. When the component (D) is used together with the component (A) described above, examples of the component (D) include ionic compounds that can react with the component (A) to form a cationic transition metal compound.

Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarboundeborate and the like can be mentioned, and among 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 trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Examples of amine cations include ammonium cations. Specific examples of ammonium cations include trimethylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations (for example, tri (n-butyl) ammonium cations). N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and the like N, N-dialkylanilinium cation; diisopropylammonium Examples thereof include dialkylammonium cations such as cations and dicyclohexylammonium cations. 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, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

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

The component (D) can be used singly or in combination of two or more. In addition, when the component (D) is used together with the component (A) described above, the amount used is preferably 0.1 to 10 times mol and about 1 times mol to the component (A). Is more preferable.

(E) Halogen Compound The component (E) is a halogen-containing compound which is a Lewis acid (hereinafter also referred to as “(E-1) component”), a complex compound of a metal halide and a Lewis base (hereinafter referred to as “(E -2) component ”) and an organic compound containing an active halogen (hereinafter also referred to as“ component (E-3) ”), for example, the rare earth element compound or component (A) above By reacting with a reactant with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is insufficiently charged can be produced.

As the component (E-1), for example, an element of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 in the Periodic Table A halogen compound containing can be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable.
Specific examples of the halogen-containing compound that is the Lewis acid include methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, Diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, tri (pentafluorophenyl) Luminium, tri (pentafluorophenyl) borate, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among these, diethylaluminum chloride, Particularly preferred are ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide.
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, etc., and these Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferable. Magnesium chloride, chloride Ngan, zinc chloride, copper chloride being particularly preferred.
As the Lewis base constituting the component (E-2), phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols and the like are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol, lauryl alcohol are preferred.
The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
The component (E-2) may be used alone or in combination of two or more.

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

The component (E) can be used singly or as a mixture of two or more. In addition, when the component (E) is used together with the component (A), the amount used is preferably 0 to 5 times mol, more preferably 1 to 5 times mol relative to 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, substituted or unsubstituted fluorene. The said (F) component may be used individually by 1 type, and may be used in combination of 2 or more type.

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 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) Indene, (1-benzyl-3-t-butyldimethylsilyl) indene and the like can be mentioned, and 3-benzyl-1H-indene and 1-benzyl-1H-indene are particularly preferable from the viewpoint of reducing the molecular weight distribution.

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

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. Thereby, since the bulk height as a polymerization catalyst increases advantageously, reaction time can be shortened and reaction temperature can be made high. Moreover, 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, substituted indene, and substituted fluorene include a hydrocarbyl group and a metalloid group, and the hydrocarbyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. It is preferably 1 to 8, and more preferably. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

The component (F) can be used alone or in combination of two or more. In addition, from the viewpoint of improving the catalytic activity, the amount of the component (F) used is preferably more than 0 as a molar ratio with respect to the component (A) when used together with the component (A). More preferably, it is more preferably 1, or more, more preferably 3 or less, further preferably 2.5 or less, and particularly preferably 2.2 or less.

The above-mentioned components (A) to (F) are preferably combined in various ways and used in the polymerization step as a catalyst composition. Suitable catalyst compositions include the following first catalyst composition and second catalyst composition.

The first catalyst composition includes the component (A-1), the component (B), and the component (D), and further includes the component (C) and the component (E) as optional components. It is preferable to include one or more components. In the case where 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 the component (C) and the component (E) as optional components. ) Component and at least one of the component (F). In addition, when a 2nd catalyst composition contains (F) component, catalyst activity improves.

The coupling step is a step of performing a reaction (coupling reaction) for modifying at least a part (for example, terminal) of the 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) dioctyl tin (IV); Examples include isocyanate compounds such as 4,4′-diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like. 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 from the viewpoint of reaction efficiency and low gel formation.
In addition, 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 according to the purpose. Examples thereof include methanol, ethanol, isopropanol, and the like. When a catalyst derived from a Lewis acid is used as a polymerization catalyst. Can be used in particular by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) to these solvents. The amount of the acid to be added is preferably 15 mol% or less with respect to the solvent. Above this, the acid remains in the copolymer, which may adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of catalyst residue in the copolymer can be suitably reduced.

The content of the multi-component copolymer (a1) in the rubber component (a) is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 100% by mass, and 15 to 100% by mass. The range of is more preferable. If the content of the multi-component copolymer (a1) in the rubber component (a) is 10% by mass or more, the effect of the multi-component copolymer (a1) is sufficiently exhibited, and the abrasion resistance of the vulcanized rubber composition. The nature is further improved.

There is no restriction | limiting in particular as rubber components other than the said multicomponent copolymer (a1) in the said rubber component (a), According to the objective, it can select suitably, For example, natural rubber (NR), 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 Etc. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

Furthermore, the rubber composition preferably contains a void introducing agent (b) from the viewpoint of providing a plurality of voids in the vulcanized rubber composition of the present invention. When the rubber composition contains the void introducing agent (b), the surface roughness of 5 to 100 μm can be more reliably formed in the vulcanized rubber composition of the present invention.

Examples of the void introducing agent (b) include foaming agents, hydrophilic short fibers, metal sulfate salts, thermally expandable microcapsules, and porous cellulose particles. Among these, it is preferable to use a foaming agent from the viewpoint of adjusting the surface roughness more reliably by adjusting the average diameter of the voids of the vulcanized rubber composition. In addition, these space | gap introducing agents (b) may be used individually by 1 type, and may mix and use 2 or more types.

Here, with respect to the foaming agent, when the rubber composition is vulcanized, bubbles derived from the foaming agent are formed in the vulcanized rubber composition, voids are provided in the vulcanized rubber composition, and the vulcanized rubber composition Since a predetermined surface roughness can be formed on the object surface, the on-ice performance of the tire can be further improved.

Examples of the blowing agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DNPT), dinitrosopentastyrenetetramine, benzenesulfonyl hydrazide derivative, p, p'-oxybisbenzenesulfonylhydrazide (OBSH), ammonium bicarbonate. , Sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound, N, N′-dimethyl-N, N′-dinitrosophthalamide, toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, p, p′-oxybisbenzenesulfonyl semicarbazide Etc. Among these foaming agents, dinitrosopentamethylenetetramine (DNPT) is preferable. These foaming agents may be used individually by 1 type, and may use 2 or more types together.

The blending amount of the foaming agent is not particularly limited, but it is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the foaming agent is 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component (a), the air gap can be sufficiently formed and the on-ice performance of the tire can be further improved. Since the distortion at the time of receiving becomes large and the effect of the above-mentioned multi-component copolymer (a1) becomes large, the wear resistance of the tire can be further improved. Further, if the content of the foaming agent is 50 parts by mass or less with respect to 100 parts by mass of the rubber component (a), the foamed rubber to be generated has sufficient strength, so that the wear resistance of the tire is further improved. And a sufficient ground contact area can be secured.
* Please add 0.5 to 30 parts by weight → 1 to 20 parts by weight as the preferred range of the amount.

Furthermore, it is preferable that urea, zinc stearate, zinc benzenesulfinate, zinc white, etc. are used in combination with the foaming agent. These foaming aids may be used alone or in combination of two or more. By using a foaming aid in combination, the foaming reaction can be promoted to increase the degree of completion of the reaction, and unnecessary deterioration can be suppressed over time.
The blending amount of the foaming aid is not particularly limited, but is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component.

For the hydrophilic short fibers, a gas generated from a foaming agent or the like during the vulcanization of the rubber composition enters the inside of the hydrophilic short fibers and has a shape (void) having a shape corresponding to the shape of the hydrophilic short fibers. Since a predetermined surface roughness (unevenness) can be formed on the surface of the vulcanized rubber composition, the on-ice performance of the tire can be further improved. Moreover, the surface of the concave portion on the surface is made hydrophilic by being covered with a resin derived from hydrophilic short fibers. Therefore, when a vulcanized rubber composition comprising a rubber composition containing hydrophilic short fibers and a foaming agent is used for a tire, the wall surface of the recess is exposed on the tread surface, so the affinity with water is improved and the recess is Water can be actively taken in, the tire has excellent drainage properties, and the on-ice performance of the tire can be greatly improved.

Examples of the hydrophilic resin used as a raw material for the hydrophilic short fibers include resins having a hydrophilic group in the molecule. Specifically, a resin containing at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom is preferable. For example, —OH, —COOH, —OCOR (R is an alkyl group), —NH ₂ And a resin containing at least one substituent selected from the group consisting of —NCO and —SH. Of these substituents, —OH, —COOH, —OCOR, —NH ₂ , and —NCO are preferable. For example, ethylene-vinyl alcohol copolymer, vinyl alcohol homopolymer, poly (meth) acrylic acid or its ester, polyethylene glycol, carboxyvinyl copolymer, styrene-maleic acid copolymer, polyvinyl pyrrolidone, vinyl pyrrolidone-acetic acid Examples thereof include a vinyl copolymer and mercaptoethanol. Among these, an ethylene-vinyl alcohol copolymer, a vinyl alcohol homopolymer, and poly (meth) acrylic acid are preferable, and an ethylene-vinyl alcohol copolymer is particularly preferable.

On the surface of the hydrophilic short fiber, a coating layer made of a low melting point resin having affinity for the rubber component (a), preferably having a melting point lower than the maximum vulcanization temperature of the rubber composition. It may be formed. By forming such a coating layer, the affinity between the hydrophilic layer and the rubber component (a) is good while effectively maintaining the affinity of the hydrophilic short fiber with water. Dispersibility in a) is improved. In addition, the low melting point resin melts at the time of vulcanization to form a coating layer having fluidity, thereby contributing to adhesion between the rubber component (a) and the hydrophilic short fiber, and good drainage and durability. It is possible to easily realize a tire imparted with characteristics. The thickness of the coating layer may vary depending on the blending amount and average diameter of the hydrophilic short fibers, but is usually 0.001 to 10 μm, preferably 0.001 to 5 μm.
The melting point of the low melting point resin used for the coating layer is preferably lower than the maximum temperature for vulcanization of the rubber composition. The maximum temperature for vulcanization means the maximum temperature that the rubber composition reaches when vulcanizing the rubber composition. For example, in the case of mold vulcanization, it means the maximum temperature that the rubber composition reaches from the time when the rubber composition enters the mold to the time when the rubber composition exits the mold and cools. It can be measured by embedding a thermocouple in the rubber composition. The upper limit of the melting point of the low-melting resin is not particularly limited, but is preferably selected in consideration of the above points. Generally, it is 10 ° C. lower than the maximum vulcanization temperature of the rubber composition. Is preferable, and it is more preferably lower by 20 ° C. or more. The industrial vulcanization temperature of the rubber composition is generally about 190 ° C. at the maximum. For example, when the maximum vulcanization temperature is set to 190 ° C., the low melting point resin The melting point is usually selected within a range of less than 190 ° C, preferably 180 ° C or less, and more preferably 170 ° C or less.
The low melting point resin is preferably a polyolefin resin, and examples include polyethylene, polypropylene, polybutene, polystyrene, ethylene-propylene copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene- Examples thereof include propylene-diene terpolymers, ethylene-vinyl acetate copolymers, and ionomer resins thereof.

The content of the hydrophilic short fibers is preferably in the range of 0.1 to 100 parts by mass, more preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass in total of the rubber components. By keeping the content of the hydrophilic short fibers in the above range, a good balance between performance on ice and wear resistance can be achieved.

As for the metal sulfate, when the vulcanized rubber composition is used for a tire, it dissolves upon contact with snow and ice, and can form a plurality of voids on the surface of the tire tread. A predetermined surface roughness can be formed. When the surface of the vulcanized rubber composition has roughness (unevenness), excellent drainage properties are imparted to the tire, and the on-ice performance of the tire can be greatly improved.

Here, the metal of the sulfate metal salt is not particularly limited, but is preferably an alkali metal and / or an alkaline earth metal from the viewpoint of reliably dissolving at the time of contact with an icy and snowy road surface, for example, potassium, Examples include magnesium, calcium, and barium.

The content of the metal sulfate salt is preferably in the range of 5 to 40 parts by mass, more preferably in the range of 10 to 35 parts by mass with respect to 100 parts by mass in total of the rubber component (a). By keeping the content of metal sulfate in the above range, a good balance between performance on ice and wear resistance can be achieved.

The thermally expandable microcapsule has a property of being vaporized or expanded by heat. When the vulcanized rubber composition is used for a tire, a plurality of voids can be formed inside the vulcanized rubber composition. A predetermined surface roughness can be formed on the surface of the vulcanized rubber composition. Since the surface of the vulcanized rubber composition has roughness (unevenness), the affinity with water is improved, and the recesses on the surface of the vulcanized rubber composition can actively take in water. Excellent drainage is imparted and the on-ice performance of the tire can be greatly improved.

The thermally expandable microcapsule has a configuration in which a thermally expandable substance is encapsulated in a shell material formed of a thermoplastic resin. The shell material of the thermally expandable microcapsule can be formed of a nitrile polymer.
In addition, the thermally expandable substance encapsulated in the shell of the microcapsule has a property of being vaporized or expanded by heat. For example, at least one selected from the group consisting of hydrocarbons such as isoalkane and normal alkane is exemplified. Is done. Examples of isoalkanes include isobutane, isopentane, 2-methylpentane, 2-methylhexane, 2,2,4-trimethylpentane, etc., and normal alkanes include n-butane, n-propane, n-hexane, Examples thereof include n-heptane and n-octane. These hydrocarbons may be used alone or in combination. As a preferred form of the thermally expandable substance, a hydrocarbon which is liquid at room temperature and dissolved in hydrocarbon at room temperature is preferable. By using such a mixture of hydrocarbons, a sufficient expansion force can be obtained from the low temperature region to the high temperature region in the vulcanization molding temperature range (150 ° C. to 190 ° C.) of the unvulcanized tire.
Examples of such heat-expandable microcapsules include trade names “EXPANCEL 091DU-80” and “EXPANEL 092DU-120” manufactured by Expancel, Sweden, or trade names “Matsumoto Micro, manufactured by Matsumoto Yushi Seiyaku Co., Ltd. "Sphere F-85D" or "Matsumoto Microsphere F-100D" can be used.

The amount of the thermally expandable microcapsule is preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the rubber component (a). By keeping the blending amount of the thermally expandable microcapsules within the above range, a good balance between performance on ice and wear resistance can be achieved.

The porous cellulose particles have voids inside and can be provided in the vulcanized rubber composition so that a plurality of voids can be provided in the vulcanized rubber composition. A predetermined surface roughness can be formed on the object surface. Thereby, since the tread surface has roughness (unevenness), the affinity with water is improved, and the recesses on the surface of the vulcanized rubber composition can actively take in water, which is excellent for tires. Drainability is imparted, and the on-ice performance of the tire can be greatly improved.

Here, the porous cellulose particles refer to cellulose particles having a porous structure with a porosity of 75 to 95%. When the porosity of the porous cellulose particles is 75% or more, the effect on improving the performance on ice is excellent, and when the porosity is 95% or less, the strength of the particles can be increased. The porosity is more preferably 80 to 90%.
The porosity of the porous cellulose particles can be obtained from the following formula by measuring the volume of a sample having a constant mass (ie, porous cellulose particles) with a graduated cylinder and determining the bulk specific gravity.
Porosity [%] = {1− (bulk specific gravity of sample [g / ml]) / (true specific gravity of sample [g / ml])} × 100
The true specific gravity of cellulose is 1.5.

The particle size of the porous cellulose particles is not particularly limited, but those having an average particle size of 1000 μm or less are preferably used from the viewpoint of wear resistance. Although the minimum of an average particle diameter is not specifically limited, It is preferable that it is 5 micrometers or more. The average particle diameter is more preferably 100 to 800 μm, and further preferably 200 to 800 μm.

Further, as the porous cellulose particles, spherical particles having a major axis / minor axis ratio of 1 to 2 are preferably used. By using particles having such a spherical structure, it is possible to improve dispersibility in the rubber composition and contribute to improvement of performance on ice and maintenance of wear resistance. The ratio of major axis / minor axis is more preferably 1.0 to 1.5.
The average particle diameter of the porous cellulose particles and the ratio of major axis / minor axis can be obtained, for example, from an image obtained by observing the porous cellulose particles with a microscope. In the observation image, the major axis and minor axis of the particles (if the major axis and minor axis are the same, the length in a certain axial direction and the length in the axial direction perpendicular thereto) are measured for 100 particles, and the average value is calculated. By calculating, the average particle diameter can be obtained, and the ratio of the major axis / minor axis can be obtained by the average value obtained by dividing the major axis by the minor axis.
Such porous cellulose particles are commercially available, for example, as “Visco Pearl” from Rengo Co., and are described in JP-A No. 2001-323095 and JP-A No. 2004-115284. It can be used suitably.

The content of the porous cellulose particles is preferably in the range of 0.3 to 20 parts by mass with respect to 100 parts by mass of the rubber component (a). When the content is 0.3 parts by mass or more, the effect of improving the performance on ice can be enhanced, and when the content is 20 parts by mass or less, the rubber hardness can be prevented from becoming excessively high. Abrasion deterioration can also be suppressed. The content of the porous cellulose particles is more preferably 1 to 15 parts by mass, and further preferably 3 to 15 parts by mass.

The rubber composition preferably further contains a resin component (c). When the rubber composition contains the resin component (c), the workability of the rubber composition is further improved. Moreover, since the rubber composition contains the resin component (c) together with the multi-component copolymer (a1), high wear resistance derived from the multi-component copolymer (a1) is maintained, and molding of a tire or the like is performed. In some cases, it is possible to provide a rubber composition having excellent tackiness when bonded to other members, leading to an improvement in productivity of tires and the like.

As the resin component (c), various natural resins and synthetic resins can be used. Specifically, rosin resins, terpene resins, petroleum resins, phenol resins, coal resins, xylene resins. It is preferable to use a resin or the like. These resin components (c) may be used individually by 1 type, and may use 2 or more types together.

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

In the synthetic resin, the petroleum-based resin is 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, for example, thermal decomposition of naphtha in the petrochemical industry. Is obtained by polymerizing with a Friedel-Crafts catalyst in the form of a mixture. Examples of the petroleum-based resin, a C ₅ fraction obtained by thermal cracking of naphtha (co) polymer obtained by aliphatic petroleum resin (hereinafter sometimes referred to as "C ₅ resins".), Naphtha of the C ₉ fraction obtained by thermal decomposition (co) polymer obtained by aromatic petroleum resin (hereinafter sometimes referred to as "C ₉ resins".), wherein the C ₅ fraction and C ₉ fraction Copolymer petroleum resin obtained by copolymerization of the components (hereinafter sometimes referred to as “C ₅ -C ₉ resin”), alicyclic compound petroleum resin such as hydrogenated or dicyclopentadiene Styrene resin such as styrene, substituted styrene, or a copolymer of styrene and another monomer.

C ₅ fractions obtained by thermal decomposition of naphtha are usually olefins such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene and 3-methyl-1-butene. These include hydrocarbons, diolefin hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 3-methyl-1,2-butadiene and the like. Further, aromatic petroleum resin obtained by C ₉ fraction (co) polymerization, vinyl toluene, a resin obtained by polymerizing an aromatic carbon atoms 9, indene major monomers, by thermal cracking of naphtha Specific examples of the C ₉ fraction obtained include styrene homologues such as α-methylstyrene, β-methylstyrene, and γ-methylstyrene, and indene homologues such as indene and coumarone. Trade names include Petrogin made by Mitsui Petrochemical, Petlite made by Mikuni Chemical, Neopolymer made by Nippon Petrochemical, Petol made by Toyo Soda, etc.

Furthermore, in the present invention can be in terms of workability, it is suitably used modified petroleum resin modified petroleum resin comprising the C ₉ fraction. 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 Can be mentioned.

Preferred unsaturated alicyclic compounds include cyclopentadiene, methylcyclopentadiene and the like. Further, as the unsaturated alicyclic compound, a Diels-Alder reaction product of alkylcyclopentadiene is also preferable. And tricyclopentadiene. As the unsaturated alicyclic compound, dicyclopentadiene is particularly preferable. Dicyclopentadiene-modified C ₉ petroleum resin in the presence of dicyclopentadiene and C ₉ fraction both can be obtained by thermal polymerization or the like. Examples of the dicyclopentadiene-modified C ₉ petroleum resin, for example, Neo polymer 130S (manufactured by Nippon Petrochemicals).

Examples of the compound having a hydroxyl group include alcohol compounds and phenol compounds. Specific examples of the alcohol compound include 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. Also, the C ₉ petroleum resin having a hydroxyl group, after introduction of the ester group in the petroleum resin by thermal polymerization with petroleum distillate (meth) acrylic acid alkyl ester, a method of reducing the ester group, petroleum resin It can be produced by a method of hydrating the double bond after remaining or introducing the double bond therein. 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 resins, obtained by cationic polymerization of the C ₉ fraction in the presence of phenol, modified is easy and low cost. 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. Typical examples of such ethylenically unsaturated carboxylic acids include (anhydrous) maleic acid, fumaric acid, itaconic acid, tetrahydro (anhydrous) phthalic acid, (meth) acrylic acid or citraconic acid. Unsaturated carboxylic acid-modified C ₉ petroleum resin can be obtained by thermally polymerizing C ₉ petroleum resin and ethylenically unsaturated carboxylic acid. In the present invention, maleic acid-modified C ₉ petroleum resin is preferable. Examples of the unsaturated carboxylic acid-modified C ₉ petroleum resin, for example, Neo Polymer 160 (manufactured by Nippon Petrochemicals).

Further, it 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, it is preferably a C ₉ fraction obtained by thermal cracking of naphtha. Specific examples include TS30, TS30-DL, TS35, TS35-DL, etc., from the STRILL series manufactured by SCHILL & SEILACHER.

In the synthetic resin, examples of the phenolic resin include alkylphenol formaldehyde resins and rosin-modified products thereof, alkylphenolacetylene resins, modified alkylphenol resins, terpenephenol resins, and the like. Hitachi Chemical Co., Ltd.), and p-tert-butylphenol acetylene resin colesin (BASF).

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

The resin component (c) preferably has an SP value of 4 or less, and more preferably 3 or less. If the SP value of the resin component (c) is 4 or less, it can be suppressed that the resin component (c) is locally present in the rubber composition and becomes a fracture nucleus, and the abrasion resistance of the vulcanized rubber composition The nature is further improved. The lower limit of the SP value of the resin component (c) is not particularly limited, but is preferably 0.01 or more.
Here, the SP value of the resin component (c) means a solubility parameter calculated using Hansen's formula, and more specifically, among the three parameters of Hansen, the dipole mutual relationship between molecules. It means a value calculated from the energy of action and the energy of hydrogen bonds.

The resin component (c) preferably has a weight average molecular weight (Mw) of 2000 or less, more preferably 1500 or less. If the weight average molecular weight (Mw) of the resin component (c) is 2000 or less, it can be suppressed that the resin component (c) is locally present in the rubber composition and becomes a fracture nucleus. Abrasion resistance is further improved. The lower limit of the weight average molecular weight (Mw) of the resin component (c) is not particularly limited, but is preferably 400 or more.
Here, the weight average molecular weight (Mw) of the resin component (c) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

The resin component (c) is preferably a resin having a softening point of 200 ° C. (measurement method: ASTM E28-58-T) or less, more preferably in the range of 80 ° C. to 150 ° C., 90 The range of from 0 to 120 ° C. is even more preferable. When the softening point is 200 ° C. or less, the temperature dependence of the hysteresis loss characteristic is small, and the workability is further improved.

Further, the resin component (c) is preferably contained in an amount of 5 to 150 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the rubber component (a). The content is more preferably 80 parts by mass, and particularly preferably 20 to 50 parts by mass. When the content of the resin component (c) is 5 parts by mass or more with respect to 100 parts by mass of the rubber component (a), the tackiness of the rubber composition and the wear resistance of the vulcanized rubber composition are further improved. And if it is 150 mass parts or less, workability | operativity of a rubber composition can be maintained favorable.

The rubber composition preferably further contains a softening agent (d). It is because workability | operativity of a rubber composition improves because a rubber composition contains a softening agent (d).

Examples of the softener include mineral-derived mineral oil, petroleum-derived aromatic oil, paraffinic oil, naphthenic oil, and natural product-derived palm oil. Among these, from the viewpoint of crack resistance of the rubber composition, a mineral-derived softener and a petroleum-derived softener are preferable.

Among the above-mentioned, the softener is particularly preferably a mixture of naphthenic oil and asphalt or paraffinic oil.
Here, in the mixture of naphthenic oil and asphalt, the naphthenic oil may be a hydrogenated naphthenic oil, and the hydrogenated naphthenic oil is preliminarily hydrogenated by a high-temperature high-pressure hydrorefining technique. It can be obtained by chemical purification. On the other hand, the asphalt content is preferably 5% by mass or less from the viewpoint of compatibility with the rubber component (a) and the effect as a softening agent. In addition, an asphaltene component is quantified from the composition analysis measured based on JPI method (Japan Petroleum Institute method).

In the rubber composition of the present invention, the softener (d) preferably has an SP value of 4 or less, and more preferably 3 or less. If the SP value of the softening agent (d) is 4 or less, it can be suppressed that the softening agent (d) is locally present in the rubber composition and becomes a fracture nucleus, and the crack resistance of the rubber composition is reduced. Further improvement is achieved, and the fracture resistance is improved. In addition, although it does not specifically limit as a minimum of SP value of a softening agent (d), It is preferable that it is 0.01 or more.
Here, the SP value of the softening agent (d) means a solubility parameter calculated using Hansen's formula, and more specifically, among the three parameters of Hansen, the dipolar interaction between molecules. A numerical value calculated from the energy of action and the energy of hydrogen bonds.

The softener (d) preferably has a weight average molecular weight (Mw) of 2000 or less, more preferably 1500 or less. If the weight average molecular weight (Mw) of the softening agent (d) is 2000 or less, it is possible to suppress the softening agent (d) from being locally present in the rubber composition and becoming a fracture nucleus, and the rubber composition The crack resistance of the object is further improved. In addition, although it does not specifically limit as a minimum of the weight average molecular weight (Mw) of a softening agent (d), It is preferable that it is 400 or more.
Here, the weight average molecular weight (Mw) of the softening agent (d) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In addition, the content of the softening agent (d) is preferably 0.1 to 150 parts by weight, more preferably 1 to 130 parts by weight with respect to 100 parts by weight of the rubber component (a). 5 to 110 parts by mass is even more preferable. When the content of the softening agent (d) is 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (a), the workability of the rubber composition is further improved, and at 150 parts by mass or less. If present, the crack resistance of the rubber composition is further improved.

The rubber composition preferably further contains a filler (e). When the rubber composition contains a filler (e), the reinforcing property and wear resistance of the vulcanized rubber composition of the present invention can be improved. The filler (e) is not particularly limited, and carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, oxidation Magnesium, titanium oxide, potassium titanate, barium sulfate, and the like can be mentioned. Among these, carbon black, silica, and aluminum hydroxide are preferable, and carbon black and silica are more preferable. These may be used alone or in combination of two or more.

Examples of the carbon black include GPF, FEF, HAF, ISAF, and SAF grade carbon black.
Examples of the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among these, wet silica is preferable.
Moreover, as said aluminum hydroxide, it is preferable to use Heidilite (trademark, product made by Showa Denko) etc.

The content of the filler (e) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 120 parts by mass with respect to 100 parts by mass of the rubber component (a), Is more preferably from 100 to 100 parts by weight, particularly preferably from 30 to 80 parts by weight. When the content of the filler is 10 parts by mass or more, the effect of improving the reinforcing property by the filler can be sufficiently obtained, and when it is 120 parts by mass or less, good workability can be maintained. it can.

Furthermore, it is preferable that the rubber composition further contains a silane coupling agent in order to improve the effect of the silica. The silane coupling agent is not particularly limited, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, and bis (3-triethoxysilylpropyl). ) Disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpro -N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothia Zolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl -N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably in the range of 2 to 20 parts by mass, more preferably in the range of 5 to 15 parts by mass with respect to 100 parts by mass of the silica. When the content of the silane coupling agent is 2 parts by mass or more with respect to 100 parts by mass of silica, the effect of silica is sufficiently improved, and the content of the silane coupling agent is 20 with respect to 100 parts by mass of silica. If it is below mass parts, the possibility of gelation of the rubber component (a) is low.

Furthermore, it is preferable that the rubber composition contains a crosslinking agent. There is no restriction | limiting in particular as this crosslinking agent, According to the objective, it can select suitably. Examples thereof 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 type crosslinking agent (vulcanizing agent) is more preferable among these crosslinking agents.
The content of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component (a).

When using the vulcanizing agent, a vulcanization accelerator can be used in combination. Examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate, and xanthate compounds.

In addition, the rubber composition may include a vulcanization aid, a colorant, a flame retardant, a lubricant, a plasticizer, a processing aid, an antioxidant, an anti-aging agent, an anti-scorch agent, an anti-UV agent, if necessary. Other components such as an antistatic agent, an anti-coloring agent, and other compounding agents can be contained depending on the purpose of use.

<Tire tread>
The tire tread of the present invention is characterized by using the above-described vulcanized rubber composition of the present invention. Since the tire tread of the present invention uses the vulcanized rubber composition described above, when applied to a tire, the tire tread is excellent in both on-ice performance and wear resistance of the tire.

<Tire>
The tire of the present invention includes the above-described tire tread of the present invention. Since the tire of the present invention uses the above-described tire tread, it is excellent in both on-ice performance and wear resistance. The tire of the present invention is particularly useful as a winter tire such as a studless tire because it is excellent in both on-ice performance and wear resistance.
The tire of the present invention may be obtained by vulcanization after molding using an unvulcanized rubber composition according to the type and member of the tire to be applied, and uses a semi-vulcanized rubber that has undergone a preliminary vulcanization process or the like. After molding, it may be further vulcanized. In addition, as gas with which a tire is filled, inert gas, such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.

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

<Method for analyzing copolymer>
The number average molecular weight (Mn), weight average molecular weight (Mw) and 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)
Monodisperse polystyrene was analyzed by gel permeation chromatography [GPC: HLC-8121GPC / HT manufactured by Tosoh Corporation, column: GMH _HR -H (S) HT × 2 manufactured by Tosoh Corporation, detector: differential refractometer (RI)]. As a reference, the polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer were determined. 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 using a ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard). : 6 ppm) from the integration ratio of each peak.

(3) Melting point ( _Tm )
Using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, “DSCQ2000”), the melting point of the copolymer was measured based on JIS K 7121 (1987).

(4) Endothermic peak energy Using a differential scanning calorimeter (DSC, manufactured by T.A. Instruments Japan, "DSCQ2000"), an increase of 10 ° C / min in accordance with JIS K 7121 (1987) The temperature was increased from −150 ° C. to 150 ° C. at a temperature rate, and the endothermic peak energy at 0 to 120 ° C. at that time (1st run) was measured.

(5) Glass transition temperature (Tg)
Using a differential scanning calorimeter (DSC, manufactured by TS Instruments Japan, "DSCQ2000"), the glass transition temperature (Tg) of the copolymer is measured according to JIS K 7121 (1987). did.

(6) Crystallinity The crystal melting energy of 100% crystalline polyethylene and the melting peak energy of the obtained copolymer were measured, and the crystallinity was calculated from the energy ratio of polyethylene and 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 synthesized copolymer was measured for ¹³ C-NMR spectrum.

<Synthesis Method of Ternary Copolymer>
To a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 160 g of styrene and 600 mL of toluene were added.
Mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amidogadolinium complex {1,3-[(t-Bu)) in a glass container in a glove box under a nitrogen atmosphere 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 obtain 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 further 80 mL of a toluene solution containing 20 g of 1,3-butadiene was charged into the pressure resistant stainless steel reactor over 8 hours. Copolymerization was carried out for 5 hours.
Next, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 mass% isopropanol solution 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 vacuum-dried at 50 ° C. 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 ), Endothermic peak energy, glass transition temperature (Tg), and crystallinity were measured by the above methods. The results are shown in Table 1.
Further, 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. The polymer was confirmed to have a main chain consisting only of an acyclic structure.

<Synthesis Method of Binary Copolymer>
After adding 2,000 g of a toluene solution containing 120 g (2.22 mol) of 1,3-butadiene to a sufficiently dry 4 L stainless steel reactor, ethylene was introduced at 1.72 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol was placed in a glass container. , 28.5 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 2.00 mmol of diisobutylaluminum hydride are dissolved in 40 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution is taken out from the glove box, an amount of 25.0 μmol in terms of gadolinium is added to the monomer solution, and polymerization is performed at 50 ° C. for 90 minutes. After the polymerization, 5 ml of 2,2′methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was further added with a large amount of methanol. Separate and vacuum dry at 70 ° C. to obtain a binary copolymer.
About the obtained binary copolymer, number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), ethylene unit, content of butadiene unit, melting point ( _Tm ), endothermic peak energy The glass transition temperature (Tg) and the crystallinity are measured by the above methods. The results are shown in Table 1.

<Production and evaluation of vulcanized rubber composition>
According to the formulation shown in Table 2, a rubber composition was produced using a normal Banbury mixer. The obtained rubber composition was vulcanized at 160 ° C. for 15 minutes to prepare samples of vulcanized rubber compositions of Comparative Examples 1 to 5 and Examples 1 to 5.
Moreover, according to the compounding prescription shown in Table 2, a rubber composition is manufactured using a normal Banbury mixer. The obtained rubber composition is vulcanized at 160 ° C. for 15 minutes to prepare samples of the vulcanized rubber compositions of Comparative Examples 6 and 7.
With respect to each of the obtained samples, the surface roughness and the porosity were measured by the following method, and the wear resistance and the performance on ice were further evaluated. The results are shown in Table 2.

(8) Surface roughness The samples of the vulcanized rubber compositions of Comparative Examples 1 to 5 and Examples 1 to 5 were measured for surface roughness: Ra (μm) according to JIS B 0601 (2001). .
Further, surface roughness: Ra (μm) is measured for samples of the vulcanized rubber compositions of Comparative Examples 6 and 7 in accordance with JIS B 0601 (2001).

(9) Porosity After the samples of the vulcanized rubber compositions of Comparative Examples 1 to 5 and Examples 1 to 5 were cut at arbitrary locations, the weight of each cut sample was measured using a dense electronic balance. The difference from the theoretical weight ((theoretical weight−measured weight) × 100) was defined as the porosity (%).
Further, the samples of the vulcanized rubber compositions of Comparative Examples 6 and 7 were cut at an arbitrary position, and then the weight of each cut sample was measured using a dense electronic balance, and the difference from the theoretical weight ((theoretical Weight−measured weight) × 100) is defined as the porosity (%).

(10) Abrasion resistance With respect to the samples of the vulcanized rubber compositions of Comparative Examples 1 to 5 and Examples 1 to 5, the amount of wear was measured according to the B method of the sliding wear test of JIS K 7218 (1986). . The measurement temperature was room temperature (23 ° C.) and the load was 16N.
Moreover, about the sample of the vulcanized rubber composition of the comparative examples 6 and 7, the amount of wear is measured according to the B method of the sliding wear test of JIS K 7218 (1986). The measurement temperature is room temperature (23 ° C.) and the load is 16N.
The evaluation was expressed as an index with the reciprocal of the wear amount of the vulcanized rubber of Comparative Example 5 being 100. The larger the index value, the smaller the wear amount and the better the wear resistance.

(11) Performance on ice When the vulcanized rubber composition samples of Comparative Examples 1 to 5 and Examples 1 to 5 were formed into test pieces having a diameter of 50 mm and a thickness of 10 mm, they were pressed against fixed ice and rotated. The generated frictional force was detected by a load cell, and the dynamic friction coefficient μ was calculated. The measurement temperature was −2 ° C., the surface pressure was 12 kgf / cm ² , and the sample rotation peripheral speed was 20 cm / sec.
In addition, with respect to the samples of the vulcanized rubber compositions of Comparative Examples 6 and 7, after forming into a test piece having a diameter of 50 mm and a thickness of 10 mm, the frictional force generated when rotating by pressing on fixed ice was detected by a load cell. Then, the dynamic friction coefficient μ is calculated. The measurement temperature is −2 ° C., the surface pressure is 12 kgf / cm ² , and the sample rotation peripheral speed is 20 cm / sec.
The evaluation was expressed as an index with the dynamic friction coefficient μ of Comparative Example 5 as 100. The larger the index value, the larger the dynamic friction coefficient μ, indicating better performance on ice.

* 1 Natural rubber: TSR20
* 2 Butadiene rubber: Product name “BR01” manufactured by JSR Corporation
* 3 Ternary copolymer: Ternary copolymer synthesized by the above method * 4 Binary copolymer: Binary copolymer synthesized by the above method * 5 Carbon black: SAF grade carbon black, Asahi Carbon Product name "ASAHI # 105"
* 6 Process oil: Petroleum hydrocarbon process oil, manufactured by Idemitsu Kosan Co., Ltd., trade name "DAIAANA PROCESS OIL NS-28"
* 7 Silica: Tosoh Silica Industry Co., Ltd., trade name “Nipsil AQ”
* 8 Silane coupling agent: Bistriethoxysilylpropyl polysulfide, manufactured by Shin-Etsu Chemical Co., Ltd. * 9 Wax: Microcrystalline wax, manufactured by Seiko Chemical Co., Ltd. * 10 Anti-aging agent: Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK 6C”
* 11 Resin: Aliphatic hydrocarbon resin, manufactured by Mitsui Petrochemical Co., Ltd., trade name “HI-REZ G-100X”
* 12 Hydrophilic short fibers: Hydrophilic short fibers produced by the following method In accordance with Production Example 3 disclosed in JP2012-219245A, two twin screw extruders were used and polyethylene was used as a hopper [manufactured by Nippon Polyethylene, Novatec. 40 parts by mass of HJ360 (MFR 5.5, melting point 132 ° C.)] and 40 parts by mass of an ethylene-vinyl alcohol copolymer [manufactured by Kuraray, Eval F104B (MFR 4.4, melting point 183 ° C.)] are charged from the die outlet. Each of the fibers was extruded at the same time, and the fibers obtained according to a conventional method were cut into a length of 2 mm to produce hydrophilic short fibers in which a coating layer made of polyethylene was formed on the surface of a core made of an ethylene-vinyl alcohol copolymer. .
* 13 Zinc oxide: manufactured by Hakusuitec Co., Ltd. * 14 Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller CZ”
* 15 Vulcanization accelerator MBTS: Di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM-P”
* 16 Foaming agent: dinitrosopentamethylenetetramine, manufactured by Sankyo Kasei Co., Ltd., trade name "Cermic AN"

From Table 2, it can be seen that the vulcanized rubber compositions of the examples according to the present invention have both high performance on ice and wear resistance at a high level.

10 Vulcanized rubber composition 20 Void

Claims

The rubber component is a vulcanized rubber composition comprising a multi-component copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit,
A vulcanized rubber composition, wherein the vulcanized rubber composition has a surface roughness of 5 to 100 μm.
2. The rubber composition according to claim 1, wherein the vulcanized rubber composition has a plurality of voids and has a porosity of 10 to 80%.
The multi-component 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 a content of the aromatic vinyl unit of 2 to 35 mol%. The vulcanized rubber composition according to claim 1 or 2, wherein the vulcanized rubber composition is%.
The vulcanized rubber composition according to any one of claims 1 to 3, wherein the multi-component copolymer has a melting point of 30 to 130 ° C as measured by a differential scanning calorimeter (DSC).
5. The multi-component copolymer according to claim 1, wherein the endothermic peak energy measured with a differential scanning calorimeter (DSC) at 0 to 120 ° C. is 10 to 150 J / g. The vulcanized rubber composition as described.
6. The vulcanized rubber composition according to claim 1, wherein the multi-component copolymer has a glass transition temperature of 0 ° C. or less as measured by a differential scanning calorimeter (DSC). .
The vulcanized rubber composition according to any one of claims 1 to 6, wherein the multi-component copolymer has a crystallinity of 0.5 to 50%.
The vulcanized rubber composition according to any one of claims 1 to 7, wherein in the multi-component copolymer, the non-conjugated olefin unit is an acyclic non-conjugated olefin unit.
The vulcanized rubber composition according to claim 8, wherein the multi-component copolymer is such that the non-cyclic non-conjugated olefin unit is composed only of an ethylene unit.
10. The vulcanized rubber composition according to claim 1, wherein the aromatic vinyl unit of the multi-component copolymer includes a styrene unit.
The vulcanized rubber composition according to any one of claims 1 to 10, wherein in the multi-component copolymer, the conjugated diene unit includes a 1,3-butadiene unit and / or an isoprene unit.
The vulcanized rubber composition according to any one of claims 1 to 11, wherein the content of the multi-component copolymer in the rubber component is 5 to 100% by mass.
The vulcanized rubber composition according to any one of claims 1 to 12, wherein the vulcanized rubber composition further contains a void introducing agent.
The void-introducing agent is at least one selected from the group consisting of foaming agents, hydrophilic short fibers, metal sulfate salts, thermally expandable microcapsules, and porous cellulose particles. Vulcanized rubber composition.
A tire tread characterized by using the vulcanized rubber composition according to any one of claims 1 to 14.
A tire comprising the tire tread according to claim 15.