JP2014214204A - Thermoplastic elastomer composition and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic thermoplastic elastomer composition which is excellent in performance as a thermoplastic elastomer, e.g. heat resistance and mechanical characteristics, and is producible by an economically excellent method.SOLUTION: A thermoplastic elastomer composition contains a branched olefinic copolymer which comprises a principal chain consisting of a copolymer of ethylene, an α-olefin and a diene and a side chain(s) originated from a crystalline propylene polymer containing a vinyl group at one terminal, in a diene content of the principal chain of 0.1-10 mol%. Its production method is also provided.

Description

  The present invention relates to a branched structure olefin copolymer having a main chain composed of a copolymer of ethylene, α-olefin and diene, and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end. The present invention relates to a thermoplastic elastomer composition and a method for producing the same.

  The thermoplastic elastomer refers to an elastomer that is softened by heating and has fluidity, and has rubber elasticity when cooled. Specifically, the elastomer is melted at the processing temperature at the time of the molding process, and can be easily molded by a method used for well-known resin molding, but after the molding process, the temperature actually used as various materials ( (Hereinafter referred to as “use temperature”), it is an industrially very useful material having the same physical properties as crosslinked rubber.

Conventionally, polymers such as block copolymers, particularly various multi-block copolymers such as triblock copolymers are known as thermoplastic elastomers.
In general, the block copolymer has a structure in which a “soft segment” having amorphous or rubbery physical properties and a “hard segment” in a crystalline state or a glass state are combined at a use temperature of a typical thermoplastic elastomer. . The polymer chains in the hard segment become bonded to each other at typical service temperatures and become elastomeric. However, when heated at a temperature higher than the melting temperature of the hard segment (hereinafter also abbreviated as “Tm”) or the glass transition temperature of the hard segment (hereinafter also abbreviated as “Tg”), the polymer easily undergoes thermoplastic behavior. Will come to show.
The use temperature of the thermoplastic elastomer is typically around room temperature, for example, in the range of 10 ° C. to 40 ° C., but depending on the use environment and application, the temperature is lower (for example, 0 ° C. or lower) or higher (for example, 50 ° C. or higher). ) Is expected, and heat resistance may be required. In that case, the thermal properties of the hard segment become important.

Well-known thermoplastic elastomer (TPE) compositions include styrenic block copolymers (SBC), such as linear chains such as styrene-isoprene-styrene triblock copolymers and styrene-butadiene-styrene triblock copolymers. Triblock copolymers are mentioned.
These copolymers are known to exhibit a relatively good balance between heat resistance and elastomeric properties because they have a well-controlled block structure and the styrene segment has a relatively high Tg. However, since these styrenic block copolymers are usually produced by sequential anionic polymerization or chemical coupling of linear diblock copolymers, the types of monomers that can be used are limited. Further, each polymer chain requires a stoichiometric amount of a polymerization initiator, and the polymerization reaction rate is relatively slow, so that the process is not economical.
Furthermore, the typical glass transition temperature of SBC is about 80 to 90 ° C., and therefore, the use of these copolymers is limited because it has fluidity again and poor heat resistance at higher use temperatures.

Dynamically cross-linked thermoplastic elastomer (TPV) compositions are also known. The dynamically crosslinked thermoplastic elastomer composition is characterized by a sea-island structure in which crosslinked rubber particles, which are thermosetting elastomers, are finely dispersed as domains (island phases) in a crystalline thermoplastic matrix (sea phase). It is a multiphase polymer material. At normal temperature, the domain imparts the function of vulcanized rubber to the TPV composition, and at a high temperature, the thermoplastic matrix flows and can be plastically deformed. Therefore, the molding process similar to that of the thermoplastic is possible. These materials are used in many applications where vulcanized rubber is used, such as hoses and gaskets.
A TPV composition is typically crosslinked by mixing a crosslinkable elastomer containing a diene or the like with a suitable crosslinking agent while mixing inside a mixer or a molding machine. Thus, the crosslinked rubber particles are formed while being finely dispersed in the thermoplastic matrix.

A great many types of TPV compositions are known, but the most widely used at present are the crystalline polypropylene resin (PP) phase as the thermoplastic matrix and the ethylene-propylene-diene monomer as the domain ( EPDM) is an olefinic TPV composition having a phase. Centering on this olefinic TPV composition, improvement of physical properties of the TPV composition has been studied.
Specifically, the rubbery elasticity of the EPDM phase is increased by increasing the degree of crosslinking in the EPDM phase, for example, increasing the amount of diene added, increasing the amount of the crosslinking agent, or increasing the crosslinking reaction time. In addition to the effect of the improvement, the formation of a graft bond between the PP phase and the EPDM phase further improves the rubbery elasticity due to the effect of improving the interfacial adhesive strength between the domains / matrixes. However, improvements in rubbery elasticity and heat resistance are still needed.

  In order to compensate for these disadvantages of the prior art, it is possible to produce these block copolymers or thermoplastic elastomer compositions by insertion of olefin monomers using transition metal compounds or by coordination polymerization to improve process efficiency and raw material economy. In view of the above, improvement of physical properties by an olefin block copolymer, specifically, a propylene block copolymer is being studied.

  In Non-Patent Document 1, the mechanical properties of these propylene-based block copolymers are evaluated in detail. According to this, the Tm of the propylene segment is higher than the Tg of the polystyrene segment of the aforementioned styrenic block copolymer, thereby having higher elastomeric properties than the styrenic block copolymer, especially at high temperatures. However, a living polymerization catalyst is used in producing these propylene block copolymers. The living polymerization catalyst can theoretically obtain only one polymer chain from one catalyst molecule, the productivity is limited, and the use is limited to a relatively small amount of high value-added fields.

  Therefore, a method for producing a “block-like copolymer” by a method with higher productivity has been studied. As a specific “block-like copolymer”, a method of forming a graft copolymer having different side chain and main chain properties by copolymerizing a polymer having a vinyl group capable of coordination polymerization at one end and a monomer Is being considered.

  Patent Document 1 discloses an olefinic thermoplastic elastomer composition having specific physical properties, including a branched olefin copolymer obtained by copolymerizing a polymerizable macromonomer in a soft segment, and a method for producing the same.

  Patent Document 2 discloses a thermoplastic elastomer composition containing a branched olefin polymer having an isotactic polypropylene segment as a crystalline side chain and an atactic polypropylene as an amorphous main chain, and a method for producing the same. .

  Patent Document 3 discloses a composition containing a branched propylene copolymer having an isotactic polypropylene segment in the side chain and a propylene ethylene copolymer in the main chain.

JP-T-2001-527589 JP-T-2001-525463 International Publication No. 2008/059969

Proceedings of the National Academy of Sciences (2006) vol. 103 (42) pp. 15327

  However, in the branched olefin copolymer described in Patent Document 1, although the Tm of the side chain is higher than the Tg of SBC, it is lower than that of crystalline polypropylene and the heat resistance is still not sufficient. The elastomer composition disclosed in Patent Document 1 has been further tested by the present inventors. As a result, it has been found that the elastomer properties are clearly insufficient. The branched olefin copolymer described in the document has an ethylene copolymer as a main chain and an ethylene homopolymer as a side chain, but an ethylene polymer side chain can be crystallized between side chains. Even after crystallization, the side chains are likely to slip, and the function as a physical cross-linking point is insufficient. Therefore, it is considered that the mechanical properties as an elastomer are inferior.

  Further, the branched olefin polymer described in Patent Document 2 uses atactic polypropylene as a main chain portion. However, it is generally known that atactic polypropylene has a high glass transition point, which is known to be around 0 ° C., is brittle at low temperatures, and is typically used as a thermoplastic elastomer at low temperatures due to addition to crystalline resins. The impact resistance improvement effect cannot be expected. In addition, atactic polypropylene is generally known to have very high compatibility with isotactic polypropylene, and when added to a crystalline polypropylene matrix, it changes the structure of the matrix itself and deteriorates mechanical properties such as rigidity. I will let you. Moreover, since the affinity between the main chain and the side chain is high, the interaction between the side chains cannot be sufficient, and the mechanical properties as an elastomer cannot be said to be sufficient.

  The invention described in Patent Document 3 is mainly related to fluidity improvement and impact resistance improvement, and there is no disclosure of an elastomer. The macromonomer disclosed in Patent Document 3 and actually produced has a high molecular weight, and the proportion of crystalline propylene including the macromonomer that is not actually copolymerized in the branched propylene copolymer is large. It is clear that the performance as is not intended.

  It is also known that the rubbery elasticity of the elastomer of the TPV composition is greatly affected by the degree of cross-linking, and further increases the degree of cross-linking of the domains and produces graft bonds between the thermoplastic matrix / domains. It is known that rubbery elasticity is further improved. On the other hand, if the degree of cross-linking is increased until a graft bond between the thermoplastic matrix / domain is formed, bonds in the thermoplastic matrix are mainly broken by peroxides, resulting in a decrease in heat resistance and deterioration of the resin. There are many harmful effects such as coloring associated with, and there is a limit to the effect of improving physical properties by the crosslinking method.

  In view of the above problems, the present invention provides an olefinic thermoplastic elastomer composition that is excellent in performance as a thermoplastic elastomer, such as heat resistance and mechanical properties, and that can be produced by an economically excellent method. Let it be an issue.

As a result of intensive studies to solve the above problems, the present inventor has found that a composition containing an ethylene-α-olefin-diene terpolymer having a highly crystalline polypropylene segment as a side chain is thermoplastic. It has been found that it has very high performance as an elastomer.
The thermoplastic elastomer composition of the present invention having highly crystalline polypropylene as a side chain has a side chain component (one piece) that forms a hard segment as compared with a thermoplastic elastomer derived from a linear or branched olefin copolymer according to the prior art. Even if the content of the component (derived from the crystalline propylene polymer containing a vinyl group at the terminal) is relatively low, it exhibits excellent elastomeric properties, and is particularly flexible and excellent in elastic recovery. This is considered to be due to the fact that the highly crystalline polypropylene side chain exhibits a particularly excellent action as a physical cross-linking point. Also, the combination of the highly crystalline polypropylene side chain and the ethylene terpolymer main chain This is considered to be due to the fact that specific and excellent characteristics are exhibited.

  That is, the gist of the present invention is as follows.

[1] A branched structure olefin copolymer having a main chain composed of a copolymer of ethylene, α-olefin and diene and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end is included. A thermoplastic elastomer composition, wherein the diene content in the main chain is 0.1 mol% or more and 10 mol% or less.

[2] The thermoplastic elastomer composition according to [1], wherein the diene is a diene having 4 to 20 carbon atoms.

[3] The thermoplastic elastomer composition according to [1] or [2], wherein the α-olefin content in the main chain is 5 mol% or more and 70 mol% or less.

[4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the crystalline propylene polymer has an isotactic pentad fraction of 0.80 or more.

[5] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the crystalline propylene polymer has a syndiotactic pentad fraction of 0.60 or more.

[6] The thermoplastic elastomer composition according to any one of [1] to [5], wherein the crystalline propylene polymer has a number average molecular weight of 50,000 or less.

[7] The thermoplastic elastomer composition according to any one of [1] to [6], wherein a glass transition point of the thermoplastic elastomer composition is −30 ° C. or lower.

[8] The thermoplastic elastomer composition according to any one of [1] to [7], wherein a density of the thermoplastic elastomer composition is 0.880 g / mL or less.

[9] The thermoplastic elastomer composition contains the crystalline propylene polymer and the components derived from the crystalline propylene polymer in a total amount of 30% by weight or less, [1] to [8] The thermoplastic elastomer composition according to any one of the above.

[10] The thermoplastic elastomer composition according to any one of [1] to [9], wherein the elongation at break of the thermoplastic elastomer composition is 500% or more.

[11] The thermoplastic elastomer composition according to any one of [1] to [10], wherein the thermoplastic elastomer composition exhibits an elastic recovery rate of 70% or more upon recovery from 300% elongation. .

[12] It has a main chain made of a copolymer of ethylene, α-olefin and diene, and a side chain derived from a crystalline propylene polymer having a vinyl group at one end and a number average molecular weight of 50,000 or less. A method for producing a thermoplastic elastomer composition containing a branched olefin copolymer, wherein the following (a) to (d) components are mixed in the presence of a transition metal catalyst in the main chain: (D) A method for producing a thermoplastic elastomer composition comprising a polymerization step in which the following components (a) to (d) are coordinately polymerized so that the diene content is 0.1 mol% or more and 10 mol% or less.
(A) a crystalline propylene polymer having a vinyl group at one end, an isotactic pentad fraction of 0.80 or more, and a number average molecular weight of 50,000 or less (b) ethylene (c) at least 1 3 or more kinds of α-olefins (d) of at least one kind and 4 to 20 carbon atoms of a diene.

[13] A main chain composed of a copolymer of ethylene, α-olefin and diene, and a side chain derived from a crystalline propylene polymer having a vinyl group at one end and a number average molecular weight of 50,000 or less. A method for producing a thermoplastic elastomer composition containing a branched olefin copolymer, wherein the following (a ′) to (d) components are mixed in the presence of a transition metal catalyst in the main chain: (D) The manufacturing method of a thermoplastic elastomer composition including the polymerization process which coordinates-polymerizes the following (a ')-(d) component so that diene content may be 0.1 mol% or more and 10 mol% or less.
(A ′) a crystalline propylene polymer having a vinyl group at one end, a syndiotactic pentad fraction of 0.60 or more, and a number average molecular weight of 50,000 or less (b) ethylene (c) at least 1 or more types of C3-C20 alpha olefin (d) At least 1 type of C4-C20 diene

[14] The method for producing a thermoplastic elastomer composition according to [12] or [13], wherein the transition metal catalyst is a complex represented by the following general formula (I).

(In General Formula (I), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, and T ¹ is a divalent group containing 1 to 30 atoms other than hydrogen atoms. R ² is a Lewis base. A heteroaryl group having 5 to 20 carbon atoms, wherein the heteroaryl group may have a substituent, M ¹ is a Group 4 metal of the periodic table, and X ¹ is monoanionic, dianion X represents the number of X ¹ groups and is an integer of 0 to 5. R ² and M ¹ may be bonded to each other to form a ring. (In the figure, a solid line represents a bond, a broken line represents an arbitrary bond, and an arrow represents a coordination bond.)

[15] In the mixing step, mixing is performed so that the content of the component (a) is 30% by weight or less of the total amount of the components (a) to (d). ] The manufacturing method of the thermoplastic elastomer composition of description.

[16] In the mixing step, mixing is performed so that the content of the component (a ′) is 30% by weight or less of the total amount of the components (a ′) to (d) [13] or [14] The method for producing a thermoplastic elastomer composition according to [14].

[17] In the production method, polymerization is performed so that a total of the crystalline propylene polymer and the components derived from the crystalline propylene polymer in the thermoplastic elastomer composition is 30% by weight or less. The method for producing a thermoplastic elastomer composition according to any one of [12] to [16].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the thermoplastic elastomer excellent in mechanical characteristics, such as heat resistance, elongation at break, and an elastic recovery rate, by an economical manufacturing method.

  Hereinafter, embodiments of the present invention will be described in more detail. However, the description of the constituent elements described below is an example of embodiments of the present invention, and the present invention is not limited to these, and the gist thereof Various modifications can be made within the range described above.

  The thermoplastic elastomer composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) contains a main chain composed of a copolymer of ethylene, α-olefin and diene, and a vinyl group at one end. A thermoplastic elastomer composition containing a branched olefin copolymer having a side chain derived from a crystalline propylene polymer (hereinafter, sometimes referred to as “branched olefin copolymer of the present invention”). is there.

The composition of the present invention has a diene content of a copolymer of ethylene, α-olefin and diene (hereinafter referred to as “diene content in the main chain”), which is the main chain of the branched structure olefin copolymer that is a constituent thereof. However, it is 0.1 mol% or more and 10 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less, and further preferably 0.5 mol% or less. When the diene content in the main chain exceeds the above upper limit, when the branched olefin copolymer of the present invention is crosslinked, the degree of crosslinking becomes too large, and when the composition of the present invention is added to the crystalline resin, the matrix A coarse gel may be generated without being finely dispersed therein. As a result, physical properties may deteriorate and appearance may become a problem. On the other hand, when the diene content in the main chain is less than the lower limit, sufficient crosslinking may not occur and the elastomer physical properties of the composition may not be improved.
Here, the diene content in the main chain is a constitutional unit derived from all monomers constituting the copolymer of ethylene, α-olefin and diene, which is the main chain of the branched structure olefin copolymer of the present invention. It is a percentage of the proportion of structural units derived from diene.
The diene content in the main chain and the α-olefin content in the main chain described later can be measured by ¹ H-NMR and ¹³ C-NMR.

The composition of the present invention may have any other configuration as long as it includes the branched structure olefin polymer having the main chain and the side chain. And those showing physical properties.
-The diene which comprises the principal chain of the branched structure olefin type copolymer of this invention is a C4-C20 diene.
The α-olefin content of the copolymer of ethylene, α-olefin and diene, which is the main chain of the branched structure olefin polymer of the present invention (hereinafter sometimes referred to as “α-olefin content in main chain”). It is 5 mol% or more and 70 mol% or less.
Here, the α-olefin content in the main chain is a constitutional unit derived from all monomers constituting the copolymer of ethylene, α-olefin and diene, which is the main chain of the branched structure olefin copolymer of the present invention. It is the percentage of the proportion of structural units derived from α-olefins.
-The isotactic pentad fraction of the crystalline propylene polymer from which the side chain of the branched olefin polymer of the present invention is derived is 0.80 or more.
-The syndiotactic pentad fraction of the crystalline propylene polymer from which the side chain of the branched structure olefin polymer of the present invention is derived is 0.60 or more.
-The number average molecular weight of the crystalline propylene polymer from which the side chain of the branched olefin polymer of the present invention is derived is 50,000 or less.
-The glass transition point of the composition of this invention is -30 degrees C or less.
-The density of the composition of this invention is 0.880 g / mL or less.
-In the composition of this invention, the component derived from a crystalline propylene polymer and a crystalline propylene polymer is contained 30weight% or less in total.
-The elongation at break of the composition of this invention is 500% or more.
-The composition of the present invention exhibits an elastic recovery rate of 70% or more upon recovery from 300% elongation.

  These constituent features of the present invention will be described in more detail.

<Branched structure olefin copolymer>
The composition of the present invention contains the branched olefin copolymer of the present invention as a constituent component.
The branched olefin copolymer is a crystalline propylene polymer (hereinafter referred to as “crystalline”) having a main chain of a copolymer of ethylene, α-olefin and diene and a side chain containing a vinyl group at one end. It may be referred to as “polypropylene macromonomer”.

Although the physical property value of the said branched structure olefin type copolymer is not specifically limited, Usually, it has melting | fusing point derived from a crystalline polypropylene macromonomer. These preferred values are similar to those preferred for the crystalline polypropylene macromonomer, but may differ from the melting point of the crystalline polypropylene macromonomer.
The molecular weight of the branched structure olefin copolymer of the present invention is not particularly limited, but the weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography), preferably 200,000 or more. Yes, more preferably 300,000 or more. However, since this branched structure olefin copolymer usually exists in the polymerization product as a mixture with unreacted raw materials, it is practically impossible to isolate it and evaluate its molecular weight alone. . Therefore, this molecular weight is evaluated as the molecular weight of the whole composition described later.

(Main chain: Copolymer of ethylene, α-olefin and diene)
The main chain of the branched structure olefin copolymer of the present invention is a copolymer of ethylene, α-olefin and diene.
The copolymer of ethylene, α-olefin and diene corresponds to a “soft segment” having amorphous or rubbery physical properties in the thermoplastic elastomer composition of the present invention. The main chain is usually low crystalline and preferably amorphous so as to suit the domain characteristics of the “soft segment”.

  The type of the copolymer of ethylene, α-olefin and diene used as the main chain is not particularly limited. Specifically, (b) ethylene and (c) at least one carbon number. It is a copolymer obtained by copolymerizing 3 to 20 α-olefin and (d) at least one kind of C 4-20 diene, and in particular, from the viewpoint of process, economy and physical properties, (b A copolymer obtained by copolymerizing ethylene), (c-1) at least one or more types of α-olefin having 3 to 8 carbon atoms, and (d-1) at least one type of diene having 8 to 20 carbon atoms. Polymers are preferred.

  The α-olefin used in the main chain is more preferably propylene, 1-butene, 1-hexene or 1-octene, more preferably propylene or 1-butene, and particularly preferably propylene.

The diene used for the main chain is not particularly limited as long as it has two or more double bonds in the monomer molecule, and may be either a conjugated diene or a non-conjugated diene. It may be linear or branched, and may have a cyclic structure in the molecule.
The diene is not particularly limited, but is usually a diene having 4 to 20 carbon atoms, and a diene having 8 to 20 carbon atoms is preferable.
As a preferable diene, one having a structure easily copolymerized (for example, a terminal vinyl group or a norbornene skeleton) is preferable in terms of reactivity. In addition, the reaction selectivity of the double bond part in the diene is high, that is, of the two double bonds in the diene, one double bond is consumed by copolymerization, and one double bond is contained in the polymer. What remains as a double bond is preferable because it does not crosslink at the polymerization stage.

  Specific dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 5-vinyl-2-norbornene, norbornadiene, dicyclopentadiene, cyclo Examples include hexadiene and 4-vinylcyclohexene. Particularly preferred dienes are 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene and 4-vinylcyclohexene.

  The α-olefin content contained in the copolymer of ethylene, α-olefin and diene, that is, the α-olefin content in the main chain is not particularly limited, but is usually 70 mol% or less, Preferably it is 60 mol% or less, More preferably, it is 50 mol% or less. The lower limit is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more. When the α-olefin content in the main chain exceeds the upper limit, the compatibility between the main chain and the side chain becomes too high, and the possibility that the side chains are phase separated or co-crystallized is reduced. It may be difficult to form physical crosslinking points between copolymer chains. Moreover, if it is less than the said lower limit, it will become a thing with insufficient softness | flexibility and may not be suitable for the property requested | required as an elastomer.

  Although the physical property value of the copolymer of ethylene, α-olefin and diene used as the main chain in the present invention is not particularly limited, its glass transition point (Tg) is usually −30 ° C. or less, Preferably it is -50 degrees C or less.

  The total of the α-olefin content in the main chain of the main chain composed of a copolymer of ethylene, α-olefin and diene and the diene content in the main chain is not particularly limited, but is usually 5 mol% or more, preferably 10 mol%. It is above and is usually 80 mol% or less.

  The weight average molecular weight (Mw) of the copolymer of ethylene, α-olefin and diene used as the main chain in the present invention is not particularly limited, but is preferably 200,000 or more, more preferably 300,000 or more. Since the branched olefin copolymer of the present invention contained in the composition of the present invention has a branched structure, it is practically impossible to measure the molecular weight of the portion corresponding to the main chain. By discounting the influence of side chains from the molecular weight of copolymers of ethylene, α-olefins and dienes that do not contain side chains derived from polypropylene macromonomers, and the molecular weight of actual branched structure olefin copolymers Can be evaluated.

(Side chain derived from crystalline polypropylene macromonomer)
The side chain of the branched structure olefin copolymer of the present invention contained in the composition of the present invention is derived from a crystalline propylene polymer containing a vinyl group at one end, so-called crystalline polypropylene macromonomer. It is derived from. In the thermoplastic elastomer composition of the present invention, the side chain functions as a “hard segment” that is in a crystalline state or a glass state, and is bonded to a main chain portion that is a “soft segment” to form a property as an elastomer. It is thought that will come to show. Specifically, the side chains crystallize together between molecules as “hard segments” and crosslink the main chain portions that are “soft segments”, thereby giving the composition properties as an elastomer. Polypropylene crystals are particularly rigid among other crystalline polyolefins, and therefore side chains derived from crystalline polypropylene macromonomers are considered to have particularly high performance as hard segments. Those having high stereoregularity have a high melting point and are considered to have particularly high heat resistance as compared with compositions containing SBC or polyethylene hard segments.

(Crystalline polypropylene macromonomer)
The crystalline polypropylene macromonomer used in the present invention is a polymer forming a side chain in the branched structure olefin copolymer of the present invention, and is a crystalline propylene polymer containing a vinyl group at one end.
The terminal vinyl group of the crystalline polypropylene macromonomer means that an unsaturated bond is generated at the terminal end by β-hydrogen elimination or β-methyl elimination at the terminal end of propylene polymerization. It means that three of the four substituents are hydrogen atoms. This terminal vinyl group is also called 1-propenyl group. Usually, unsaturated terminals other than this vinyl group, such as vinylidene groups and internal olefins, are difficult to insert by coordination polymerization, and when trying to copolymerize crystalline polypropylene macromonomer by coordination polymerization In particular, it is important that the terminal is a vinyl group.

  The method for producing the crystalline polypropylene macromonomer used in the present invention, specifically the component (a) or (a ′) described later, is not particularly limited, and a conventionally known method for producing a macromonomer And a method capable of efficiently producing a highly crystalline polypropylene macromonomer is preferred. More specifically, a method that is produced by the coordination polymerization of propylene using a transition metal compound and has a vinyl group at a high proportion of the terminal end of polymerization is preferable from an economical viewpoint.

For example, as a method of producing the isotactic polypropylene macromonomer, a stereorigid C2 symmetrically bridged metallocene catalyst is used, and the fact that β-methyl group elimination reaction occurs frequently by polymerizing propylene at high temperature, By introducing a vinyl group at the terminal (for example, JP-T-2001-525461), by using a complex having a bulky substituent at a specific site, or by using a complex having a heterocyclic group at a specific site , A method of producing high stereoregularity by increasing the frequency of β-methyl elimination reaction at a relatively low temperature (for example, JP-A-11-349634, JP-A-2009-299045, etc.), isotactic Vinyl chloride with functional groups that are easily eliminated, such as vinyl chloride, in propylene by a structure-selective metallocene catalyst A method in which a comonomer is copolymerized and a macromonomer having a terminal vinyl group is selectively produced by simultaneous elimination of a β-functional group at the same time as the insertion of the comonomer (Gaynor, SG Macromolecules 2003, 36, 4692-4698), , Relatively difficult β-methyl group elimination process using propylene polymerization catalyst in which 2,1-insertion of propylene is preferred (for example, late transition metal complex such as pyridyldiimine iron (II) complex) A method of introducing a terminal vinyl group via β-hydrogen elimination without passing through (Brookhart, M. et. Al. Macromolecules 1999, 32, 2120) and the like.
Among these, by using a complex having a heterocyclic group at a specific site, a method for producing while maintaining high stereoregularity by increasing the frequency of β methyl elimination reaction at a relatively low temperature (for example, JP-A-2009- No. 299045) is particularly preferable from the viewpoint of achieving both high stereoregularity and high vinyl selectivity.

As a method for producing the syndiotactic polypropylene macromonomer, a method using a non-bridged metallocene catalyst having a very bulky substituent (Resconi, L. et. Al. J. Am. Chem. Soc. 1992, 114, 1025.), a method of polymerizing propylene at a high temperature using a stereo-rigid Cs symmetrically bridged metallocene catalyst (Japanese Patent Publication No. 2001-525461), a propylene with a syndiotactic selective metallocene catalyst, and a function such as vinyl chloride that is easily released A method of producing a macromonomer having a terminal vinyl group selectively by copolymerizing a vinyl comonomer having a group and causing the β functional group to be eliminated simultaneously with the insertion of the vinyl comonomer (Kaminsky, W. et. Al. Macromol. Chem. Phys.2010, AS P), a method in which a vinyl group is selectively introduced into the end of syndiotactic polypropylene by bis (phenoxyimine) titanium complex having a specific substituent by β-hydrogen elimination from 2,1-insertion of propylene ( International Publication No. 03/025025, or Cherian, AE et al, Macromolecules 2005, 38, 6268, etc.).
Among these, from the viewpoint of achieving both high stereoregularity and high vinyl selectivity, a bis (phenoxyimine) titanium complex having a specific substituent is used, and β-hydrogen elimination from 2,1-insertion of propylene results in syndiotactic activity. A method in which a vinyl group is selectively introduced into the terminal of tic polypropylene is preferable.

  The crystalline polypropylene macromonomer usually contains a molecule having a vinyl group at one end but not having a vinyl group at the end, and may contain a molecule in which both ends are vinyl groups. Good. Preferably, one end of the macromonomer molecule is a vinyl group and the other end is an alkyl group. The method for producing the crystalline polypropylene macromonomer used in the present invention is not limited, but as described above, it is preferably produced by the coordination polymerization of propylene from the economical viewpoint. This is because, when produced by this method, the end of the crystalline polypropylene macromonomer molecule is usually an alkyl group at the start of the polymerization reaction and a vinyl group with a high probability of the end of the polymerization reaction. In this case, the possibility that both ends of the macromonomer molecule are vinyl groups is usually extremely low.

In the obtained crystalline polypropylene macromonomer, the proportion of molecules having a vinyl group at one end (t-vinyl%) is usually 50% or more, preferably 80% or more, particularly preferably 90% or more. When the t-vinyl% is less than 50%, the proportion of the crystalline polypropylene macromonomer added to the branched olefin copolymer of the present invention is small, and the performance of the copolymer as an elastomer is poor. May be sufficient.
The ratio of macromonomer molecules having a vinyl group at one end (t-vinyl%) represents the ratio of the number of molecules having a vinyl group at the end of all macromonomer molecules, and is calculated as follows. Is done.
(T-vinyl%) = [Mn-GPC] / [Mn-NMR] × 100
Here, [Mn-GPC] is the number average molecular weight measured by GPC, [Mn-NMR] is all macromonomer molecules, one end of each molecule is all vinyl group, and the other end is all alkyl group. Assuming that there is a number average molecular weight calculated from the total number of protons on the alkyl carbon other than the vinyl group.
In order to satisfy the above characteristics, the crystalline polypropylene macromonomer is produced using an appropriate catalyst and polymerization conditions as in the production method.
The crystalline polypropylene macromonomer may be a branched crystalline polypropylene macromonomer having a crystalline polypropylene side chain as long as rigidity and heat resistance are not impaired.

The structure of the crystalline polypropylene macromonomer is not particularly limited, but specifically, the polypropylene in the macromonomer has a structure with high stereoregularity. “Pentad (fraction)” is used as a factor representing the high degree of stereoregularity of polypropylene. Pentad shows the continuity of the relative arrangement of adjacent side-chain methyl groups of polypropylene, and the higher this value, the higher the stereoregularity. The isotactic pentad fraction (mmmm) is a percentage of the propylene unit at the center of a chain in which five propylene monomer units are continuously meso-bonded, expressed as a percentage. The syndiotactic pentad fraction (rrrr) is a percentage of the propylene units at the center of a chain in which five propylene monomer units are continuously racemically bonded to the total propylene units. The pentad is usually determined by ¹³ C-NMR. Specifically, it is obtained by the method described in JP-A-2003-292700. The structure of the crystalline polypropylene macromonomer used in the present invention is preferably one having a high isotactic pentad fraction (mmmm) or one having a high syndiotactic pentad fraction (rrrr). These are "hard segments" that form stronger and more highly crystallized crystals between the branched olefin copolymers, which acts as a stronger cross-linking point, resulting in superior elastomer performance It is because it is thought that it gives.

  A crystalline polypropylene macromonomer having a high isotactic pentad fraction (hereinafter sometimes referred to as an “isotactic polypropylene macromonomer”) is usually 0.80 in isotactic pentad fraction (mmmm). Above, preferably 0.90 or more. As the isotactic pentad fraction increases, the melting point increases, which is preferable in terms of further improving heat resistance. The upper limit of the isotactic pentad fraction is not particularly limited as long as the object of the present invention is not impaired, but the upper limit is usually 1.00 which is the upper limit in calculation.

  As a polypropylene macromonomer having a high syndiotactic pentad fraction (hereinafter sometimes referred to as “syndiotactic polypropylene macromonomer”), the syndiotactic pentad fraction (rrrr) is usually 0.60 or more. Yes, preferably 0.70 or more, more preferably 0.80 or more, and still more preferably 0.90 or more. As the syndiotactic pentad fraction is improved, the melting point is improved and the heat resistance is further improved, which is preferable. The upper limit of the syndiotactic pentad fraction is not particularly limited as long as the object of the present invention is not impaired, but the upper limit is usually 1.00 which is the upper limit in calculation.

  More preferable as the side chain of the branched structure olefin copolymer of the present invention is that the effect of the present invention can be obtained with a small amount of the side chain component even when the regularity is relatively low. It is a crystalline polypropylene macromonomer with a high fraction.

  The constituent component of the side chain of the branched structure olefin copolymer of the present invention may contain ethylene, an α-olefin other than propylene, or a component derived from a diene. A small amount of a heterogeneous bond that can be introduced in the process of polymerizing polypropylene and a small amount of comonomer to compensate for solubility during polymerization are acceptable as long as the rigidity and heat resistance of the side chain are not significantly impaired. In terms of maintaining the rigidity and heat resistance of the side chain, the side chain is preferably derived from a propylene homopolymer.

  The crystalline polypropylene macromonomer used in the present invention has a melting point (Tm) of usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. The melting point can be defined by differential thermal analysis (DSC) and can be used as an index of crystallinity of the crystalline polypropylene macromonomer. Amorphous or low-crystalline polypropylene macromonomer cannot function as a hard segment that can form a physical cross-linking point, and even if it exists as a side chain in a branched structure olefin copolymer, performance as an elastomer Is not expected.

The molecular weight of the crystalline polypropylene macromonomer used in the present invention is not particularly limited, but can be arbitrarily adjusted to obtain a composition having the desired physical and mechanical properties.
The molecular weight of the crystalline polypropylene macromonomer is based on the terminal vinyl group quantified by ¹ H-NMR spectrum. In the crystalline polypropylene macromonomer molecule, one end of each molecule is all vinyl group and the other end is all It is obtained from the total number of protons on carbon (sp ³ carbon) other than the vinyl group when it is assumed to be an alkyl group. The number average molecular weight (Mn) of the macromonomer is usually 50000 or less, preferably 30000 or less, more preferably 10,000 or less. Moreover, it is 1000 or more normally, Preferably it is 3000 or more. If the molecular weight of the crystalline polypropylene macromonomer exceeds the above upper limit, the number of macromonomer molecules significantly decreases with respect to the weight of the macromonomer used in the polymerization reaction, and as a result, it is introduced into the branched structure olefin copolymer. The number of side chains is significantly reduced. In order for the composition of the present invention to exhibit the function as an elastomer, at least two or more side chains per main chain of the branched structure olefin copolymer molecule of the present invention, that is, two or more physical physics. However, since the number of side chains decreases, a sufficient number of physical crosslinking points in the branched structure olefin copolymer may not be obtained. There is. In addition, if the molecular weight of the crystalline polypropylene macromonomer used in the present invention is less than the lower limit, entanglement between side chains becomes difficult, and the growth of physical cross-linking points between polymer chains is not promoted. Elastomer performance may be reduced.

  The molecular weight distribution of the crystalline polypropylene macromonomer used in the present invention is not particularly limited, but the side chain molecular weight distribution is preferably as narrow as possible in order to enable precise physical property control by the side chain molecular weight. The molecular weight distribution of the crystalline polypropylene macromonomer used in the present invention is usually 1 or more and 6 or less, preferably 3 or less in terms of Mw / Mn.

The amount of the side chain derived from the crystalline propylene macromonomer contained in the branched structure olefin copolymer of the present invention is not particularly limited, but it is a branched structure olefin copolymer in terms of raw material (macromonomer). Is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less, based on the total amount of all monomers constituting More preferably, it is 30% by weight or less. When this ratio is less than the lower limit, there are substantially few copolymer chains including side chains, and physical crosslinking between polymer chains tends to be difficult to form. If the upper limit is exceeded, the flexibility of the entire composition tends to be poor, and it may not be suitable for the properties required as a thermoplastic elastomer.
The elastomer composition of the present invention exhibits a function as an elastomer even if the side chain derived from the crystalline polypropylene macromonomer has a relatively low content. Therefore, it is possible to produce a composition that has high heat resistance and high elastomer performance while being extremely flexible and having a low density, which is impossible with conventional polyolefin-based elastomers.

The number of side chains contained in one polymer main chain of the branched structure olefin copolymer of the present invention is not particularly limited, but usually two or more are preferable. By having two or more side chains, this branched structure olefin copolymer is considered to function as an interpolymer chain bridge having elasticity and to exhibit a function as an elastomer. However, since there is usually a distribution in the number of side chains per main chain, it is practically impossible to accurately estimate the number of each side chain, and the number is expressed as an average value. The evaluation of the number of side chains per main chain is based on the method of evaluating the number of side chains actually bonded to the main chain by ¹³ C-NMR, or in the branched structure olefin copolymer by ¹ H-NMR. There is a method of calculating the number from the amount of incorporated macromonomer, more simply a method of calculating from the charged amount of macromonomer and the number average molecular weight of the branched olefin copolymer, and any method can be used. The branched olefin copolymer of the present invention can be characterized.

<Thermoplastic elastomer composition>
(1) Constituent Component The thermoplastic elastomer composition of the present invention contains the following branched olefin copolymer (hereinafter sometimes referred to as “(E) component”).
(E) Branched structure olefin copolymer having a main chain composed of a copolymer of ethylene, α-olefin and diene and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end The other components of the composition are not particularly limited as long as the physical properties of the object of the present invention are satisfied, but usually include the following components (F) and (G) (hereinafter, These may be referred to as “(F) component” and “(G) component”, respectively).
(F) Copolymer of ethylene, α-olefin and diene (G) Crystalline polypropylene macromonomer

Among these, the component (E) corresponds to the branched olefin copolymer of the present invention described above as <Branched olefin copolymer>.
Component (F) usually corresponds to a polymer in which no macromonomer is incorporated into the copolymer of ethylene, α-olefin and diene produced in the synthesis reaction of the copolymer (E) component, and only the main chain component. To do.
The component (G) usually corresponds to an unreacted macromonomer that has not been incorporated in the synthesis reaction of the copolymer (E) component. The macromonomer added to the reaction system of the synthesis reaction of the component (E) is usually taken in as a side chain of the component (E) or contained in the thermoplastic elastomer composition of the present invention as the component (G).
The weight ratio of the macromonomer incorporated into the component (E) and the component (G) is not particularly limited, and is appropriately adjusted so as to satisfy the target physical properties.
There are no particular limitations on the proportions of the components (E), (F), and (G) contained in the composition of the present invention, but they are arbitrarily adjusted to satisfy the desired physical properties. Preferably, the content of the component (F) and the component (G) is small, and more preferably, the composition of the present invention is composed only of the component (E).

  Even if the composition of this invention containing the said (E)-(G) component is obtained as a result of the copolymerization reaction at the time of manufacture of (E) component as above-mentioned, (E)-(G) The components may be synthesized and mixed independently, but those obtained as a result of the copolymerization reaction during the production of the component (E) are preferred from the standpoint of ease of production.

Components derived from the crystalline polypropylene macromonomer and the crystalline polypropylene macromonomer contained in the composition of the present invention, ie, the crystalline polypropylene macromonomer introduced as a side chain in the component (G) and the component (E) The total content of the components derived from the monomers is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less. On the other hand, this content is preferably 1% by weight or more, particularly preferably 5% by weight or more.
Components derived from the crystalline polypropylene macromonomer and the crystalline polypropylene macromonomer contained in the composition of the present invention, ie, the crystalline polypropylene macromonomer introduced as a side chain in the component (G) and the component (E) When the total content of the components derived from the monomers exceeds the above upper limit, the flexibility of the entire composition tends to be poor, and may not be suitable for properties required as a thermoplastic elastomer. Moreover, if it is less than the said minimum, there will be few copolymer chains containing a side chain substantially, and there exists a tendency for the physical bridge | crosslinking between polymer chains to be hard to be formed.

(2) Physical properties Since the composition of the present invention is evaluated as a physical property value as a mixture of the component (E), the component (F), and the component (G), the component (E) is usually used. It has a glass transition point derived from a copolymer of ethylene, α-olefin and diene which is a main chain and is also the component (F) itself, and is a side chain of the component (E), and the component (G) itself It also has a melting point derived from a crystalline polypropylene macromonomer.

  The glass transition point (Tg) of the composition of the present invention is usually −30 ° C. or lower, preferably −50 ° C. or lower. Since the glass transition point of the composition of the present invention depends on the glass transition point of the component (F), it usually has a glass transition point in the same range as the component (F). Depending on the composition ratio or the like, the glass transition point may not match. In addition, since the melting point of the composition of the present invention depends on the melting point of the component (G), the melting point of the crystalline polypropylene macromonomer usually has a melting point in the same range as the preferred value. Depending on the composition ratio in the composition, the melting point of the crystalline polypropylene macromonomer may not match.

Although the molecular weight of the composition of this invention is not specifically limited, A weight average molecular weight (Mw) is measured by GPC, Preferably it is 200,000 or more, More preferably, it is 300,000 or more.
Further, the branched structure olefin copolymer and the copolymer of ethylene, α-olefin, and diene (component (E) and component (F)) are sufficiently more than the crystalline polypropylene macromonomer (component (G)). When the molecular weight is high, the two components can be separated and evaluated in the molecular weight measurement by GPC. In that case, the number average molecular weight (Mn) corresponding to the branched structure olefin copolymer and the copolymer of ethylene, α-olefin and diene (component (E) and component (F)) can be evaluated, This value is not particularly limited, but is usually 100,000 or more, preferably 200,000 or more, usually 1 million or less, preferably 800,000 or less.

  The physical properties of the composition of the present invention as an elastomer are described in, for example, Proceedings of the National Academy of Sciences (2006) vol. 103 (42) pp. 15327 (Non-Patent Document 1 mentioned above), Experimental Section, or Macromolecules 2008, 41, 9548-9555.

  The density of the composition of the present invention is not particularly limited, but is usually 0.880 g / mL or less, preferably 0.875 g / mL or less, more preferably 0.870 g / mL or less. . If the density exceeds the above upper limit, flexibility tends to be poor, and particularly in compounding with isotactic polypropylene, which is an important application of thermoplastic elastomer compositions, the effect of improving impact resistance is reduced and miscibility is reduced. It may cause physical properties such as whitening. The lower limit is not particularly limited as long as the object of the present invention is not impaired.

The composition of the present invention is a thermoplastic elastomer composition having high rubber-like elasticity.
Specifically, it is a composition showing a high elongation at break, and is not particularly limited, but usually shows an elongation at break of 500% or more, preferably 700% or more, more preferably 800% or more.
The higher the elongation at break, the better the performance as an elastomer. However, when the elongation is less than the lower limit, the elastomer may be used in applications that require a particularly high deformation rate.

  The composition of the present invention has a high elastic recovery rate. Specifically, although not particularly limited, the elastic recovery rate at the time of recovery from 300% elongation is usually 70% or higher, preferably 75% or higher. The higher the elastic recovery rate, the better the performance as an elastomer. However, if the elastic recovery rate is less than the lower limit of the elastic recovery rate at the time of recovery from the 300% elongation, the performance as a general elastomer may be insufficient.

(Method for producing thermoplastic elastomer composition)
(1) Method for Producing Thermoplastic Elastomer Composition The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited as long as the desired composition can be obtained. Ethylene, α-olefin and diene A branched olefin copolymer (E) having a main chain composed of a copolymer and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end, and usually (F) ethylene , Α-olefin and diene copolymer, and (G) a crystalline polypropylene macromonomer. Specifically, the components (E) to (G) are synthesized and mixed to form a composition, or the component (E) is produced to produce the components (E) and (E). And a method of forming a composition of the component (G), which is a reaction raw material, and the component (F), which is a reaction byproduct.

In the production of the composition of the present invention, the production efficiency is advantageous. Usually, the following (a) to (d) components are mixed, and in the presence of a transition metal catalyst, (d And a polymerization step in which the following components (a) to (d) are coordinately polymerized so that the diene content is 0.1 mol% or more and 10 mol% or less.
(A) a crystalline propylene polymer having a vinyl group at one end, an isotactic pentad fraction of 0.80 or more, and a number average molecular weight of 50,000 or less (b) ethylene (c) at least 1 3 or more types of α-olefins having 3 to 20 carbon atoms (d) at least one type of diene having 4 to 20 carbon atoms

Or the following (a ′), the mixing step of mixing the components (b), (c) and (d) above, and in the presence of a transition metal catalyst, the (d) diene content in the main chain is 0.1 mol. % And 10 mol% or less, and the following (a ′) and the above-mentioned (b), (c) and a polymerization step of coordinating the component (d) are used.
(A ′) a crystalline propylene polymer having a vinyl group at one end, a syndiotactic pentad fraction of 0.60 or more, and a number average molecular weight of 50,000 or less

The component (b), the component (c), and the component (d) correspond to a raw material for forming a main chain portion in the branched structure olefin copolymer.
(B) Ethylene is not particularly limited, and refined ones and those obtained from various petrochemical plants are used. Ethylene refined in terms of quality is preferable.
(C) As a component, from a viewpoint of a process, economical efficiency, and a physical property, (c-1) at least 1 type or more C3-C8 alpha olefin is preferable.
The component (d) is preferably (d-1) at least one diene having 8 to 20 carbon atoms from the viewpoints of process, economy and physical properties.

(A) A component may be used individually by 1 type, or may use 2 or more types together although an isotactic pentad fraction and a number average molecular weight differ.
As the component (a ′), one type may be used alone, or two or more types having different syndiotactic pentad fractions and number average molecular weights may be used in combination.

The step of mixing the components (a) to (d) or the components (a ′) to (d) is not particularly limited, and the components are coordinated in the presence of a transition metal catalyst in the next step. Any mixing method can be selected as long as it does not interfere with the polymerization step.
The order of mixing is not particularly limited, and the above components may be charged all at once or mixed, or may be added and mixed during the polymerization reaction. Transitions used so that the diene content in the main chain of the branched structure olefin copolymer to be produced is 0.1 mol% or more and 10 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less. The mixing amount is appropriately adjusted according to the properties of the metal catalyst.
Further, preferably, the mixing amount is appropriately adjusted so that the α-olefin content in the main chain of the branched structure olefin copolymer to be produced is 5 mol% or more and 70 mol% or less.

In the step of mixing the components (a) to (d) or (a ′) to (d), the component (a) in the total amount of the components (a) to (d), or (a ′) to (a) The content of the component (a ′) in the total amount of the component (d) is not particularly limited, but is usually 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 15%. % By weight or less, more preferably 10% by weight or less, usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more.
Further, the content of the component (c) in the total amount of the components (a) to (d) or the total amount of the components (a ′) to (d) is not particularly limited, but is usually 70% by weight or less, preferably It is 60% by weight or less, more preferably 50% by weight or less, usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more.
Although this ratio is not particularly limited, it is usually a value equal to or less than the ratio of the total amount of the crystalline polypropylene macromonomer in the elastomer composition of the present invention described later. Specifically, since (b) ethylene, and (c) component is propylene or butene, it is a gas. Therefore, (b) and (c) components are usually (a) component or (a ′) component. Add more to In this case, the value becomes smaller than the ratio of the total addition amount of the crystalline polypropylene macromonomer in the elastomer composition of the present invention, and the total amount of the mixed component (b) and component (c) is not excessive and insufficient. These values are the same when fully incorporated into the chain.

(2) Polymerization step (transition metal catalyst)
The transition metal catalyst used in the polymerization step is not particularly limited, but it is sufficient to copolymerize ethylene, a desired α-olefin, and a diene, and be sufficient as a main chain portion of the branched structure olefin copolymer. Or a catalyst capable of producing a copolymer of ethylene, α-olefin and diene having the molecular weight necessary to obtain mechanical performance and incorporating a significant amount of crystalline polypropylene macromonomer. .

  As the type of catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used. Among these, in order for the produced thermoplastic elastomer composition to exhibit excellent performance, the crystalline polypropylene macromonomer that is the raw material of the side chain of the branched structure olefin copolymer of the present invention is contained in the main chain. It is preferable that the copolymer be homogeneously copolymerized. For this purpose, a homogeneous catalyst is preferably used in that a homogeneous main chain copolymer having a narrow molecular weight distribution can be produced, and a homogeneous catalyst using a transition metal complex is more preferable. .

  The transition metal complexes typically include transition metal complexes selected from Groups 3-15 of the periodic table, including one or more delocalized π-bonded ligands or multivalent Lewis base ligands. . Examples include metallocene complexes, half metallocene complexes, constrained geometry complexes and polyvalent pyridylamine complexes or other polychelated base complexes, preferably metallocene complexes.

  Specific examples of the structure of the catalyst using the transition metal complex include, for example, JP-A-9-87313, JP-A-11-166010, JP-A-2004-238387, JP-A-2006-63041, JP 2007-217284, JP 2007-238891, JP 2008-297287, WO 08/112133, WO 04/024740, WO 03/40195, WO No. 03/78480, WO 03/78483, WO 02/92610, WO 02/38628, WO 02/02577, US 2003/0004286, US application Publication No. 2004/220050, US Application Publication No. 2004/010103 US Pat. No. 6,515,155, US Pat. No. 6,555,634, US Pat. No. 6,632,0005, US Pat. No. 6,150,297, US Pat. No. 6,103,657, US Pat. No. 6,034,022, US Pat. Examples include compounds described in US Pat. No. 6,268,444, US Pat. No. 6,015,868, US Pat. No. 5,866,704, US Pat. No. 5,470,993, and the like.

  Examples of the transition metal complex preferably used in the present invention include a group 4 metal complex of the periodic table, and more preferably a complex represented by the following formula (I).

(In General Formula (I), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, and T ¹ is a divalent group containing 1 to 30 atoms other than hydrogen atoms. R ² is a Lewis base. A heteroaryl group having 5 to 20 carbon atoms, wherein the heteroaryl group may have a substituent, M ¹ is a Group 4 metal of the periodic table, and X ¹ is monoanionic, dianion X represents the number of X ¹ groups and is an integer of 0 to 5. R ² and M ¹ may be bonded to each other to form a ring. Among them, a solid line indicates a bond, a broken line indicates an arbitrary bond (that is, a bond may or may not exist), and an arrow indicates a coordinate bond.)

In the general formula (I), ^{R 1} is a hydrocarbon group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group.
T ¹ is a divalent bridging group containing 1 to 30 atoms other than hydrogen atoms. As the atoms constituting the T ^1, on which contains 1 to 30 atoms other than at least a hydrogen atom, may contain a further hydrogen atom. T ¹ is preferably a substituted methylene group having 1 or 2 substituents, or a substituted silylene group, and the substituted methylene group or substituted silylene group preferably has 1 to 20 carbon atoms. An alkyl group, a cycloalkyl group, or an aryl group;

R ² is a Lewis basic heteroaryl group having 5 to 20 carbon atoms (heteroatom-containing aryl group), preferably a pyridin-2-yl group, and the pyridin-2-yl group has a substituent. Examples of the substituent include an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, and a silyl group, and these substituents may further have a substituent. The group and cycloalkyl group may contain atoms other than carbon and hydrogen (hereinafter referred to as heteroatoms) in the structure. R ² and M ¹ may form a bond with each other.

M ¹ represents a Group 4 metal of the periodic table, preferably hafnium.
X ¹ is a monoanionic, dianionic, or neutral ligand group, preferably a monoanionic ligand group.
x represents the number of ^{X 1} groups is an integer of 0 to 5, preferably an integer of 1 to 3.
In general formula (I), a solid line represents a bond, a broken line represents an arbitrary bond (that is, a bond may or may not be present), and an arrow represents a coordinate bond.

  Examples of the transition metal complex represented by the general formula (I) include compounds represented by the following general formula (I-1). The compound represented by the general formula (I-1) is preferably a compound represented by the following general formula (I-2), more preferably the following general formula (I-3) or general formula (I-4). It is a compound represented by these. Moreover, the compound represented by the following general formula (I-1) is also preferably a compound represented by the following general formula (I-5), more preferably a compound represented by the following general formula (I-5). It is a compound represented by the following general formula (I-6).

In general formula (I-1), M ¹ , X ¹ , x, R ¹ and T ¹ are the same as defined in general formula (I).
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a heteroatom-containing alkyl group, a heteroatom-containing cycloalkyl group, aryl A group or a silyl group, and these groups may further have a substituent, and are preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, and an aryl group. Of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , two adjacent ones may be bonded to each other, thereby forming a condensed ring.

In general formula (I-2), M ¹ , X ¹ and x are the same as defined in general formula (I).
Each R ^a is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and preferably an alkyl group having 1 to 4 carbon atoms. These substituents may further have a substituent.
a represents the number of substituents R ^a , and the value thereof is 1 to 5, preferably 1 or 2.
The preferred ^(R _a) a, the ortho position of the two positions to the nitrogen atom are those having two ^{R a,} more preferably, ^{R a} is isopropyl or t- butyl group.
R ^c is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and aryl group further have a substituent. Also good.
R ^c may have two adjacent R ^c groups bonded to each other, thereby forming a condensed ring.
c represents the number of substituents R ^c , and the value thereof is 1 to 4.
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, or an alkyl group or aryl group having 1 to 20 carbon atoms, and may further have a substituent, preferably R ¹⁵ and R ^16. at least one is a group other than a hydrogen atom, preferably both alkyl groups R ¹⁵ and R ^16, or either one aryl group R ¹⁵ or R ^16.

In general formula (I-3) and general formula (I-4), M ¹ , X ¹ and x are the same as defined in general formula (I).
R ¹⁷ and R ¹⁸ are each independently an alkyl group having 1 to 4 carbon atoms, each of which may further have a substituent, and R ¹⁷ and R ¹⁸ are bonded to each other to form a ring. It may be.
Ar represents an aryl group having 6 to 20 carbon atoms, preferably a 2-isopropylphenyl group, a tolyl group or a fused polycyclic aryl group, more preferably a 2-isopropylphenyl group, an o-tolyl group, or a phenanthrenyl group. And more preferably a 2-isopropylphenyl group.

The following are mentioned as a particularly preferable transition metal complex represented by general formula (I-3).
[N- (2,6-di (1-methylethyl) phenyl) amido] dimethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl;
[N- (2,6-di (1-methylethyl) phenyl) amido] dimethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium di (N, N-dimethylamide);
[N- (2,6-di (1-methylethyl) phenyl) amido] dimethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dichloride;
[N- (2,6-di (1-methylethyl) phenyl) amido] diethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl;
[N- (2,6-di (1-methylethyl) phenyl) amide] diethyl (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium di (N, N-dimethylamide);
[N- (2,6-di (1-methylethyl) phenyl) amide] diethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dichloride.

Moreover, the following are mentioned as a particularly preferable transition metal complex represented by general formula (I-4).
[N- (2,6-di (1-methylethyl) phenyl) amide] (o-tolyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl;
[N- (2,6-di (1-methylethyl) phenyl) amide] (o-tolyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium di (N, N- Dimethylamide);
[N- (2,6-di (1-methylethyl) phenyl) amide] (o-tolyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dichloride;
[N- (2,6-di (1-methylethyl) phenyl) amide] (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl;
[N- (2,6-di (1-methylethyl) phenyl) amide] (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium di (N, N -Dimethylamide);
[N- (2,6-di (1-methylethyl) phenyl) amide] (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dichloride;
[N- (2,6-di (1-methylethyl) phenyl) amide] (phenanthren-5-yl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl;
[N- (2,6-di (1-methylethyl) phenyl) amide] (phenanthrene-5-yl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium di (N, N-dimethylamide);
[N- (2,6-di (1-methylethyl) phenyl) amide] (phenanthrene-5-yl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium dichloride.

In general formula (I-5), M ¹ , X ¹ and x are the same as defined in general formula (I), and R ¹⁷ and R ¹⁸ are the same as defined in general formula (I-3). , R ^c , c are the same as defined in general formula (I-2).
Each R ^b is independently an alkyl group having 1 to 4 carbon atoms, and may further have a substituent.
b represents the number of substituents R ^b , and the range thereof is 1 to 5, preferably 1 or 2.
(R ^b ) _b is preferably one substituted at two positions ortho to the nitrogen atom, more preferably an isopropyl group or a t-butyl group.
R ¹⁹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group.
c is preferably 1 or 2.

In General Formula (I-6), M ¹ is as defined in General Formula (I), and a bond, an arbitrary bond, and a coordination bond (electron pair contribution interaction) are a solid line, a broken line, and an arrow, respectively. Represented by

(Cocatalyst)
Each of the transition metal catalysts (hereinafter referred to as component [A] or paraphrased as “catalyst precursor”) is combined with various known cocatalysts, preferably cation-forming cocatalysts, strong Lewis acids or both. Thus, it can be activated to form an active catalyst composition.

In the present invention, it is usually preferable to use at least one component selected from the following components [B-1] to [B-4] as a cocatalyst (hereinafter also referred to as component [B]).
Component [B-1]: Organoaluminum oxycompound Component [B-2]: It is possible to react with the catalyst precursor and exchange it with a cation
Ionic compound component [B-3]: Lewis acid component [B-4]: Layered compound

  Specific examples of the organoaluminum oxy compound of component [B-1] include compounds represented by the following general formulas (II-1), (II-2), and (II-3).

(In the above general formulas, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ are each independently a hydrogen atom or a hydrocarbon group. And preferably represents an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, and p represents an integer of 1 to 40, preferably 2 to 30.)

  The compounds represented by the general formulas (II-1) and (II-2) are organoaluminum oxy compounds (hereinafter sometimes referred to as “aluminoxanes”), which include one or more types of trialkylaluminum, water, It is obtained by the reaction of Specifically, an aluminoxane obtained from one kind of trialkylaluminum such as methylaluminoxane and water, or two or more kinds of alkyl groups obtained from two or more kinds of trialkylaluminum such as methylethylaluminoxane and water. Examples thereof include methylaluminoxane, methylaluminoxane, methylisobutylaluminoxane, and methyl-n-octylaluminoxane.

  A plurality of the above organoaluminum oxy compounds can be used in combination. And said aluminoxane can be prepared on well-known various conditions.

The compound represented by the general formula (II-3) is 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the following general formula (II-4). It can be obtained by a reaction of ˜1: 1 (molar ratio). In general formula (II-4), R ³⁰ is a hydrogen atom or a hydrocarbon group, preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms.
_{^{R 30 -B- (OH) 2 (}} II-4)

Examples of the ionic compound capable of reacting with component [A] and converting component [A] into a cation by component [B-2] include compounds represented by the following general formula (III).
[K] ^{e +} [Z] ^e- (III)

  In general formula (III), K is a cation component, and examples thereof include a carbenium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Moreover, the cation of the metal which is easy to reduce itself, the cation of an organic metal, etc. are mentioned. Specific examples of the cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, tricyclohexylammonium, dimethyloctadecylammonium, methyldioctadecylammonium, N, N-dimethylanilinium, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver Ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferroceniu Ion and the like are included. Preferably used are triphenylcarbonium, dimethyloctadecylammonium, methyldioctadecylammonium, and N, N-dimethylanilinium.

  In the above general formula (III), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion with respect to the cationic species in which component [A] is converted. Examples of Z include organic boron compound anions such as tetraphenylboron, tetrakis (pentafluorophenyl) boron, tetrakis (nonafluorobiphenyl) boron; tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, and the like. Organoaluminum compound anions of tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, etc .; Organic phosphorus compound anions such as tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus; Tetraphenyl Organic arsenic compound anions such as arsenic and tetrakis (pentafluorophenyl) arsenic; organic antimony compounds anion such as tetraphenylantimony and tetrakis (pentafluorophenyl) antimony Down; and the like. Among these, organic boron compound anions are preferably used, and specifically, tetrakis (perfluoroaryl) boron compounds such as tetrakis (pentafluorophenyl) boron and tetrakis (nonafluorobiphenyl) boron.

  As the Lewis acid that can convert the component [B-3] into a cation, in particular, the component [A] into a cation, various organic materials such as triphenylboron, tris (pentafluorophenyl) boron, and tris (nonafluorobiphenyl) boron can be used. Boron compounds; metal halide compounds such as aluminum chloride, magnesium chloride hydride, magnesium bromide hydroxide, magnesium chloride alkoxide; solid acids such as alumina and silica-alumina; and the like are exemplified, and an organic boron compound is preferable. Includes tris (perfluoroaryl) boron such as tris (pentafluorophenyl) boron and tris (nonafluorobiphenyl) boron.

The layered compound of the component [B-4] is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and can contain exchangeable ions.
Specific examples of the layered compound include the following inorganic silicates and ion-exchangeable layered compounds.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. Examples include clay, gyrome clay, hysingelite, pyrophyllite, and ryokdeite group. These may form a mixed layer.

Examples of artificial synthetic products include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
Among these specific examples, kaolin group, halosite group, serpentine group, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and more preferably smectite, vermiculite mineral. , Synthetic mica, synthetic hectorite, synthetic saponite and synthetic teniolite, more preferably montmorillonite.

Examples of the ion-exchangeable layered compound in component [B-4] include ionic crystalline compounds having a layered crystal structure such as hexagonal close-packed type, antimony type, CdCl ₂ type, and CdI ₂ type. . Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H. ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti Examples thereof include crystalline acidic salts of polyvalent metals such as (HPO ₄ ) ₂ and γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

These [B-4] layered compounds may be used as they are, but acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , It is preferable to use after performing a salt treatment such as Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ . In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a polymer having excellent particle properties. The above components are usually used after being dehydrated and dried.

  Of the components [B-1] to [B-4], a [B-4] layered compound is preferably used, and an inorganic silicate is particularly preferably used.

(Particle carrier)
In the polymerization step of the present invention, in addition to the catalyst precursor component [A] and the cocatalyst component [B] described above, a fine particle carrier (hereinafter also referred to as component [C]) may be present as an optional component. Component [C] is composed of an inorganic or organic compound and is a fine particle carrier having a particle size of usually 5 μm or more, preferably 10 μm or more, and usually 5 mm or less, preferably 2 mm or less.

Examples of the inorganic carrier include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , ZnO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO. ₂ , composite metal oxides such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO.
Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturation such as styrene and divinylbenzene. Examples include porous polymer fine particle carriers made of (co) polymers such as hydrocarbons, etc. (where “(co) polymer” means one or both of “polymer” and “copolymer”). Sure.)

The specific surface area of these fine particle carriers is usually 20 m ² / g or more, preferably 50 m ² / g or more, and usually 1000 m ² / g or less, preferably 700 m ² / g or less.
The pore volume is usually 0.1 cm ³ / g or more, preferably 0.3 cm ³ / g or more, more preferably 0.8 cm ³ / g or more.

As the fine particle carrier, any one of various inorganic carriers and / or organic carriers exemplified above may be used alone, or two or more may be used in any combination and ratio.
The catalyst used in the polymerization step of the present invention includes the following components [A] and [B] and the optional component [C] as long as the gist of the present invention is not impaired. Other components such as component [E] may be contained.

(Organic aluminum)
In the polymerization step, an organoaluminum compound represented by the following general formula (IV) (hereinafter also referred to as component [E]) may be used as a catalyst.
AlR ³¹ _m X _3-m (IV)
(In the general formula (IV), R ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen atom, an alkoxy group, or an aryloxy group, and m is an integer of 1 to 3. is there.)

  Preferable organoaluminum compounds of component [E] are specifically trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, or halogens or alkoxys such as diethylaluminum monochloride and diethylaluminum ethoxide. Examples thereof include alkyl aluminum. You may mix and use these. Of these, trialkylaluminum, dialkylaluminum alkoxide, or alkylaluminum dialkoxide is particularly preferable. Two or more of these optional components may be used in combination.

The catalyst precursor [A] component, the cocatalyst [B] component, and the optional fine particle support [C] component and the organoaluminum [E] component are brought into contact with each other to form an active catalyst composition. It is not limited. This contact is performed not only at the time of catalyst preparation but also at the time of production of the composition of the present invention, preferably by mixing and coordination polymerization of the components (a) to (d) or the components (a ′) to (d). You may carry out in a process. The contact may be carried out in an inert gas such as nitrogen, in the polymerization reaction described later, or in a solvent. When using a solvent, it is preferable to use in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene and the like.
The contact temperature is between −20 ° C. and the solvent boiling point, and particularly preferably between room temperature and the solvent boiling point. The molar ratio of [A] component / [B] component used is preferably 1: 10,000 to 100: 1, more preferably 1: 5000 to 10: 1, most preferably 1: 1000 to 1: 1. is there.

When the organoaluminum oxy compound [B-1] is used as the [B] component, it is used at least 50 times the amount of the [A] component on a molar basis. As the [B] component, when a component other than the solid Lewis acid among the [B-2] component or the [B-3] component is used, the molar ratio to the [A] component is usually from 0.5 to 10 Preferably it is 1-6, Most preferably, it is 1-5.
When the solid Lewis acid in [B-3] or the [B-4] component is used as the [B] component, the [A] component is usually 0.0001 to 10 mmol, preferably 0. Used from 001 to 5 mmol. Further, the [E] component is optionally used in the range of 0 to 10000 mmol, preferably 0.01 to 100 mmol.

(Polymerization process)
In the polymerization step in the production method of the present invention, the conditions are not particularly limited as long as the desired product is obtained, but preferably the crystalline polypropylene macromonomer, ethylene, α-olefin and diene are simultaneously mixed with the above catalyst (active catalyst). When a composition is used, it is preferable to contact the composition. More preferably, ethylene, α-olefin and diene, and a crystalline polypropylene macromonomer are mixed in advance and the catalyst is brought into contact therewith. The crystalline polypropylene macromonomer may be added all at once before the polymerization, or may be added sequentially or continuously during the polymerization. Moreover, the process of manufacturing a crystalline polypropylene macromonomer, and the process of copolymerizing a crystalline polypropylene macromonomer with another olefin monomer and a diene monomer, and manufacturing the composition of this invention can also be performed continuously.

At this time, the total addition amount of the crystalline polypropylene macromonomer is not particularly limited, but as a result of the polymerization step, the crystalline polypropylene macromonomer and the crystalline polypropylene macromonomer are obtained in the composition of the present invention obtained. The total of the components derived from the monomers is adjusted to 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. In addition, the component derived from this macromonomer means the partial structure derived from this crystalline polypropylene macromonomer which comprises the side chain of the branched structure olefin type copolymer mentioned above as (E) component.
When the total amount of the crystalline polypropylene macromonomer exceeds the upper limit, the flexibility of the entire composition tends to be poor, and may not be suitable for the properties required as a thermoplastic elastomer. The lower limit of the total amount of the crystalline polypropylene macromonomer is not limited as long as the performance of the composition of the present invention is not impaired, but is usually 1% by weight or more, preferably 5% by weight or more. It is preferable that the amount of the crystalline polypropylene macromonomer added is small because an elastomer having high flexibility is obtained and advantageous in terms of economy.

  The crystalline polypropylene macromonomer is incorporated into the composition of the present invention after the polymerization step as a side chain component of the branched structure olefin copolymer described above as the component (E), and the component (G). As any of the unreacted macromonomers described above. That is, the total weight ratio of the crystalline polypropylene macromonomer and the components derived from the macromonomer in the composition of the present invention is the total addition amount of the crystalline polypropylene macromonomer in the production process, specifically, Is the same as the weight ratio between the charged weight of the crystalline polypropylene macromonomer expressed as the component (a) or the component (a ′) and the obtained elastomer composition.

  The reaction for producing the composition of the present invention may or may not use a solvent. Examples of the solvent used include n-pentane, n-hexane, n-heptane, n-octane, n-decane, benzene, toluene, xylene, cyclohexane, methylcyclohexane, dimethylcyclohexane and other hydrocarbons, chloroform And halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, tetrachloroethane, chlorobenzene and o-dichlorobenzene, polar solvents such as n-butyl acetate, methyl isobutyl ketone, tetrahydrofuran, cyclohexanone and dimethyl sulfoxide. it can. Among these, hydrocarbons are preferable. In addition, any one of these solvents may be used alone, or two or more may be used in any combination and ratio. When these solvents are used, they are usually removed by a known method after the completion of the reaction, and thus are not usually contained in the composition of the present invention. A very small amount of solvent may remain within the range that does not impair the physical properties.

  The thermoplastic elastomer composition of the present invention can be produced by solvent polymerization using the above-described solvents, and liquid phase solventless polymerization, gas phase polymerization, and melt polymerization that substantially use no solvent can also be used. The polymerization method may be either continuous polymerization or batch polymerization. So-called multistage polymerization in which conditions are changed in multiple stages may be employed.

  The catalyst concentration is not particularly limited. For example, when the reaction system is solution polymerization, the content of component [A] is usually 0.01 mg or more, preferably 0.05 mg or more, more preferably 0.1 mg, per liter of the reaction liquid. In addition, the range is usually 100 g or less, preferably 50 g or less, more preferably 25 g or less.

  The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually, optimum settings can be made in consideration of productivity and process capability from the following ranges. That is, the polymerization temperature is usually −70 ° C. or higher, preferably −50 ° C. or higher, more preferably −30 ° C. or higher, particularly preferably −20 ° C. or higher, and usually 150 ° C. or lower, preferably 100 ° C. or lower. It is. The polymerization pressure is usually 0.01 MPa or more, preferably 0.05 MPa or more, more preferably 0.1 MPa or more, and usually 100 MPa or less, preferably 20 MPa or less, more preferably 5 MPa or less.

The polymerization time is usually 0.1 hours or longer, preferably 0.2 hours or longer, more preferably 0.3 hours or longer, and usually 30 hours or shorter, preferably 25 hours or shorter, more preferably 20 hours or shorter, further Preferably it is the range for 15 hours or less.
In this polymerization, a molecular weight (MFR) regulator can be used so that the fluidity of the branched structure olefin copolymer to be produced is appropriate. Hydrogen is preferred as the MFR modifier.

(Dynamic cross-linked product and production method thereof)
The composition of the present invention can be used in an embodiment in which the composition is dynamically crosslinked (hereinafter referred to as a dynamically crosslinked product). Specifically, by reacting the composition of the present invention with various crosslinking agents, by performing dynamic crosslinking with the diene in the branched structure olefin copolymer of the present invention, compared to before crosslinking, Furthermore, rubber-like elasticity can be improved.
The dynamic crosslinking means that a crosslinked structure such as diene is allowed to undergo a crosslinking reaction while mixing in the presence of a crosslinking agent to form a crosslinked structure.
Thereby, the rubber-like elasticity of the composition of the present invention is further improved, and the heat resistance and oil resistance are improved.

  The method for producing the dynamically crosslinked product is not particularly limited, and specifically, there is a method in which the composition of the present invention is charged into a heated mixer and usually melt-mixed in the presence of a crosslinking agent. Can be mentioned.

  Although it does not specifically limit as a crosslinking agent, The crosslinking agent which can bridge | crosslink the main chain containing a diene, without decomposing | disassembling or crosslinking the crystalline polyolefin which the branched structure olefin copolymer of this invention has as a side chain. Can be used. Specific cross-linking agents include phenolic resins; peroxides; azides; aldehyde-amine reaction products; vinyl silane grafting agents; hydrosilylating agents; urea compounds that may have substituents; An optionally substituted guanidine; an optionally substituted xanthate; an optionally substituted dithiocarbamate; a sulfur compound such as sulfur, thiazoles, sulfenamides, and thiuramidisulfides; paraquinone Oxime compounds such as dioxime and dibenzoparaquinone dioxime are used, and phenolic resins are preferred. These may be used alone or in combination of two or more.

  The type of the mixer is not particularly limited, and for example, a rubber roll machine or a closed mixer such as a Banbury mixer can be used.

  The method for adding the crosslinking agent to the composition of the present invention is not particularly limited. Usually, the composition is heated with a mixer until the composition is in a sufficiently molten state, and then the crosslinking agent is added and mixed.

  The heating temperature is not particularly limited, but it is heated to a temperature at which the composition of the present invention is in a sufficiently molten state, usually a temperature equal to or higher than the melting point of the crystalline polypropylene macromonomer that is a side chain.

After adding a cross-linking agent to the composition of the present invention, the cross-linking reaction proceeds by subsequently mixing the melt. After mixing the composition and the crosslinking agent, the degree of crosslinking can be adjusted by following the progress of the crosslinking reaction by monitoring the required amount of mixing torque or mixing energy. The degree of mixing is not particularly limited, but it is preferable to continue mixing after the mixing torque or mixing energy curve reaches the maximum value until the secondary workability of the molten mixture is improved.
Although mixing temperature is not specifically limited, Usually, it carries out at 150 to 200 degreeC.
The mixing time is not particularly limited, but is usually 5 to 60 minutes.

  At the time of melt mixing, other elastomer components such as diene copolymer rubber and crystalline resin components such as crystalline polyolefin may be added for the purpose of improving various physical properties of the elastomer. Components such as agents and stabilizers may be added. The mixing order of these components may be mixed before melting the composition, may be mixed after melting, may be mixed after addition of the crosslinking agent, or may be mixed after addition.

  The dynamic crosslinked body is a kind of thermoplastic elastomer and can be applied to the same use and molding method as those of the thermoplastic elastomer composition of the present invention described below.

(Use of thermoplastic elastomer composition)
Since the thermoplastic elastomer composition of the present invention is excellent in flexibility, transparency, and heat resistance, various fields in which soft PVC and thermoplastic elastomer are used in addition to conventional ethylene materials and propylene materials. Can be suitably used as a simple substance, as a main component, or as an additive.
The method for molding the thermoplastic elastomer composition of the present invention or the resin composition (modified product) containing the thermoplastic elastomer composition of the present invention is not particularly limited, but for films and sheets, an inflation method applied to polyolefins, A film is formed by a T-die method, a calendar method, or the like, and a single layer or various layers of two or more layers can be appropriately provided as necessary. In the lamination, an extrusion lamination method, a heat lamination method, a dry lamination method, or the like is also possible, and the film can be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, and a tubular method. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment and the like which are usually used industrially can also be applied.

  In the case of constituting a laminate by making use of the excellent flexibility, transparency and heat resistance of the thermoplastic elastomer composition of the present invention, the materials constituting the other layers include propylene homopolymer, propylene / α-olefin Various propylene polymers such as copolymers, propylene / α-olefin block copolymers, high pressure polyethylene, ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers (EVOH), ethylene-based polymers such as ethylene-norbornene copolymer, various olefin-based copolymers such as polybutene-1 and poly-4-methylpentene-1 (TPX resin), and maleic anhydride Examples thereof include adhesive polyolefin, polyamide, polyester, and polyester elastomer.

(Applications in the field of films and sheets)
The use of the thermoplastic elastomer composition of the present invention or a modified product thereof in the field of films and sheets is not particularly limited, but examples thereof include the following uses.
That is, packaging stretch film, commercial or household wrap film, pallet stretch film, stretch label, shrink film, shrink label, sealant film, retort film, retort sealant film, heat welding film, thermal adhesive film, heat Sealing film, Bag-in-box sealant film, Retort pouch, Standing pouch, Spout pouch, Laminate tube, Heavy bag, Textile packaging film, etc. Packaging field, House film, Multi film, etc. Film field, infusion bags, high-calorie infusions and multi-chamber containers for peritoneal dialysis (CAPD), drainage bags for peritoneal dialysis, blood bags, urine bags, surgical bags, ice pillows, ampoule cases, PTP packaging, etc. Medical care Film and sheet field, civil engineering water-impervious sheet, waterproofing material, joint material, flooring, roofing, decorative film, skin film, wallpaper, etc., construction material related fields, leather, ceiling material, trunk room lining, interior skin material, vibration control Automotive parts such as seats, sound insulation sheets, display covers, battery cases, mouse pads, mobile phone cases, IC card holders, CD-ROM cases, etc., weak brushed fields, toothbrush cases, puff cases, cosmetic cases, eye drops and other pharmaceutical cases, tissues Toiletries or sanitary fields such as cases and face packs, film and sheets for stationery, clear files, pen cases, notebook covers, desk mats, keyboard covers, book covers, binders, and other office supplies, leather for furniture, beach balls, etc. Rain toys, umbrellas, raincoats, etc. General household use such as table cloth, blister package, bath lid, towel case, fancy case, tag case, pouch, amulet bag, insurance card cover, passbook case, passport case, knife case, miscellaneous goods field, retroreflective sheet, synthetic paper Etc. In addition, adhesive film is applied to the base material, and the film and sheet fields to which adhesiveness is imparted include adhesive tape, marking film, semiconductor or glass dicing film, surface protective film, steel plate / plywood protective film, automotive protective film , Adhesive tape for packaging and binding, Adhesive tape for office and home use, Adhesive tape for bonding, Adhesive tape for coating masking, Adhesive tape for surface protection, Adhesive tape for sealing, Adhesive tape for anti-corrosion and waterproof, Adhesive tape for electrical insulation, Examples include adhesive tapes for electronic devices, adhesive films, adhesive tapes for medical and hygiene materials such as a base film for banso, identification / decorative adhesive tapes, display tapes, packaging tapes, surgical tapes, and adhesive tapes for labels.

(Applications in the fields of injection molding and extrusion molding)
The use of the thermoplastic elastomer composition of the present invention or a modified product thereof in the fields of injection molding and extrusion molding is not particularly limited, but examples thereof include the following. That is, covering materials such as electric wires, cords and wire harnesses in the electric / electronic parts field, insulation sheets, control cable covering materials, airbags / covers, mudguards, bumpers, boots, air hoses, lamp packings, gaskets in automobile parts , Various malls such as window malls, site shields, weather strips, glass run channels, grommets, vibration control / sound insulation materials, home appliances, various packings in the field of weak electric power, grips, belts, rubber feet, rollers, protectors, suckers , Gaskets for refrigerators, various rolls for office automation equipment, tubular molded products such as hoses and tubes, atypical extrusions, leather-like articles, occlusion, soft tactile dolls, pen grips, toothbrush patterns General miscellaneous goods such as houseware, touch -Containers such as wear, bundling bands, infusion bottles by blow molding, bottles for food, bottles for personal care such as cosmetics, catheters for medical parts, syringes, syringe gaskets, drip tubes, tubes, ports, Caps, rubber stoppers, disposable containers and the like can be mentioned, and use by foam molding is also possible.

(Uses in the field of fibers and non-woven fabrics)
The use of the thermoplastic elastomer composition of the present invention or a modified product thereof in the fiber and non-woven fabric field is not particularly limited, but examples include the following uses. That is, by making non-woven fabric by continuous spinning, continuous crimped yarn, short fibers, monofilaments, flat yarn, melt blow method, spunbond method, sanitary materials such as disposable diapers, surgical clothes, medical supplies such as gloves, Applications include carpets, their linings and ropes. Further, canvases, tent materials, hoods, flexible containers, leisure sheets, tarpaulins, etc. by laminating these woven fabrics, monofilaments, flat yarns, slit tapes and the like with films / sheets.

(Use in reforming materials)
Since the thermoplastic elastomer composition of the present invention or a modified product thereof is excellent in affinity with polypropylene, it can be suitably used for modifying polypropylene. By the modification, in addition to flexibility, transparency, toughness, etc., heat sealability, impact resistance, affinity with additives are improved, and it can be used to improve the surface of the molded body. Moreover, hot melt adhesives, tackifiers, asphalt modification, bitumen modification, waterproof paper, etc. that make use of the heat-fusibility are also examples of applications.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to a following example, unless the summary is exceeded.
The physical property measurement, analysis, and the like in the following examples are according to the following methods.

(1) GPC measurement The number average molecular weight (Mn) of the thermoplastic elastomer composition was determined by GPC measurement. GPC measurement was performed using an Alliance GPCV2000 manufactured by Waters, and using a differential refractometer and a viscometer as a detector. As the column, four TSKgel GMH6-HT manufactured by Tosoh Corporation were used.
Ortho-dichlorobenzene was used as the mobile phase solvent and was allowed to flow out at 135 ° C. and 1.0 mL / min. The obtained data was calculated by using a monodisperse standard polystyrene manufactured by Polymer Laboratories and converting it to polyethylene from the retention time by a general calibration curve method. The numerical values used are Kpst = 1.38E-4, αpst = 0.70, Kpe = 4.77E-4, αpe = 0.70.
Unless otherwise specified, the molecular weights of the compositions in the examples are crystalline polypropylene macromonomer (component (G)), branched structure olefin copolymer component (component (E)), ethylene, α-olefin, and diene. The copolymer component (component (F)) was fractionated and evaluated as the number average molecular weight of the mixture of component (E) and component (F).

(2) DSC measurement The melting point (Tm) and the glass transition point (Tg) of the polymer were measured by DSC measurement. DSC measurement uses “Diamond DSC” manufactured by PerkinElmer, 20 ° C. for 1 minute isothermal, 10 ° C./minute to 20-210 ° C., 210 ° C. for 5 minutes, 10 ° C./minute for 210− The temperature was decreased to 70 ° C., isothermal at −70 ° C. for 5 minutes, and then determined by measurement at a temperature increase of −70 to 210 ° C. at 10 ° C./min.

(3) NMR measurement The number average molecular weight (Mn) of the crystalline propylene macromonomer containing a vinyl group at one end was measured by measuring a ¹ H-NMR spectrum and assuming that one end of all macromonomer molecules was a vinyl group. It calculated | required from the total proton number of the alkyl group in the case. Further, the stereoregularity (isotactic pentad fraction, syndiotactic pentad fraction) of the macromonomer was determined by measuring the ¹³ C-NMR spectrum of the polymer.
For the ¹ H-NMR measurement of the macromonomer, Inova 500 manufactured by Varian ( ¹ H observation frequency 500 MHz) was used. 20 mg of a sample was put into a 5 mm sample tube, and completely dissolved in 0.6 mL of orthodichlorobenzene (ODCB) -d ₄ at 120 ° C., then, 360 ° at 130 ° C., a flip angle of 45 °, and a pulse interval of 10 seconds. Accumulated. The standard of chemical shift was 7.16 ppm for the signal on the low magnetic field side of ODCB.
For the ¹³ C-NMR of the macromonomer, Inova 500 ( ¹³ C observation frequency 125.7 MHz) manufactured by Varian was used. 200 mg of a sample was put into a 10 mm sample tube and completely dissolved in 1.5 mL of orthodichlorobenzene at 120 ° C., and then 1.5 mL of heavy benzene was added and further heated. Integration was performed 2640 times under the conditions of 120 ° C., flip angle of 90 °, and pulse interval of 14.8 seconds. The standard of chemical shift was 128.06 ppm of benzene.

(4) Density measurement The density of the thermoplastic elastomer composition was measured at 23 ° C. by a water displacement method using an electronic hydrometer (“SD-200L” manufactured by Alpha Mirage).

(5) Physical property measurement The physical property values (elongation at break, strength at break, elastic recovery) of the thermoplastic elastomer composition as an elastomer were determined by evaluating the molded article of the obtained thermoplastic elastomer composition. .

(Creation of sheet (test piece))
About 5 g of the sample was press-molded at 190 ° C. and 5 MPa for about 3 minutes to prepare a sheet having a thickness of about 0.5 mm. This was cut with a dumbbell-shaped No. 8 punching blade described in JIS K6251 (vulcanized rubber tensile test method) to prepare a test piece.

(Physical property test)
The measuring device used was STA-1225 manufactured by Orientec. The distance between chucks was 20 mm, and the test piece was stretched at a rate of 15 mm / min until it broke monotonously, and the elongation and strength at break were recorded.
Further, the test piece was stretched by 300% (= 60 mm) at the same speed, and then the crosshead direction was reversed and contracted until the stress became zero at the same speed. The elongation when the stress reached zero was recorded, and the elastic recovery rate was calculated from this residual elongation.

(Production Example 1)
[Synthesis of rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (hereinafter referred to as “complex M1”)]
The complex M1 was synthesized according to the method described in Production Example M-1 of International Publication No. 2008/059969.

(Production Example 2)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer A)]
Purified hexane (1000 mL), toluene solution of methylaluminoxane (Tosoh Finechem "MMAO-3A" 2.1 mmol [Al equivalent atom] ] 6 mL was introduced. The reaction vessel was heated to 70 ° C. to saturate propylene at 0.8 MPa, and the toluene solution of the complex M1 (4.0 μmol) obtained in Production Example 1 was pumped into the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to keep the reactor pressure at 0.8 MPa. After 60 minutes, ethanol was introduced to stop the reaction. The obtained polymer was collected by filtration and dried under reduced pressure until a constant amount was obtained, to obtain 280 g of polymer. The number average molecular weight based on the terminal vinyl group measured by ¹ H-NMR of the obtained macromonomer is 9330, and the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR is 0.00. 82. The melting point (Tm) measured by DSC was 138.0 ° C.

(Production Example 3)
[Synthesis of (N-2,6-di (1-methylethyl) phenylamido) dimethyl (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)) hafnium dimethyl (complex C1)]
The complex C1 was synthesized according to the method described in International Publication No. 2008/112133, Working Example 4. The structural formula of the complex C1 is shown below.

Example 1
In a 2 L induction stirring autoclave containing a stirring blade and substituted with purified nitrogen, polypropylene macromonomer A (4.0 g) obtained in Production Example 2 and modified methylaluminoxane (“MMAO-Tosoh Finechem Co., Ltd.”) were used. 3A "2.1 mmol [Al converted atom]), 4-vinylcyclohexene (5 mL), and dry toluene (500 mL) were introduced. The reactor was heated to 100 ° C., stirred for 15 minutes, and then cooled to 35 ° C. The complex C1 (40 μmol) obtained in Production Example 3 was dissolved in toluene (6 mL) and introduced into a catalyst feeder with a rupturable plate. The reactor was heated again to 70 ° C., and a mixed gas of propylene and ethylene (propylene / ethylene = 45/55 molar ratio) was introduced to the polymerization tank up to 0.30 MPa, and then a toluene solution of complex C1 from the catalyst feeder with purified nitrogen. Was introduced to initiate the reaction. During the reaction, a mixed gas was added to keep the reactor pressure at 0.40 MPa. After a predetermined time, ethanol was introduced to stop the reaction. The gas in the reactor was released, and the reaction solution was put into ethanol to precipitate the polymer. The obtained polymer was separated by filtration, and the polymer collected by filtration was further washed with ethanol and dried under reduced pressure until a constant amount was obtained, to obtain 36.0 g of a polymer (thermoplastic elastomer composition). The 4-vinylcyclohexene content in the main chain as measured by ¹³ C-NMR was 0.4 mol%, and the propylene content was 44 mol%. Table 1 shows the physical properties of the obtained thermoplastic elastomer composition.

(Comparative Example 1)
Polymerization was carried out in the same manner as in Example 1 except that the polypropylene macromonomer A was not used, to obtain 48.9 g of a polymer (thermoplastic elastomer composition). ^The 4-vinylcyclohexene content measured by ¹³ C-NMR was 0.6 mol%, and the propylene content was 42 mol%. Table 1 shows the physical properties of the obtained thermoplastic elastomer composition.

  The thermoplastic elastomer compositions obtained in Example 1 and Comparative Example 1 were each hot-pressed at 200 ° C. using a spacer having a thickness of 0.2 mm, and allowed to cool to room temperature, thereby producing a sheet having a thickness of 0.2 mm. did. The sheet obtained from the thermoplastic elastomer composition of Example 1 showed a high elastic recovery. On the other hand, the sheet obtained from the thermoplastic elastomer composition of Comparative Example 1 did not exhibit sufficient elastic recovery.

  The composition obtained in Example 1 is a branched structure olefin copolymer having a side chain derived from a crystalline polypropylene macromonomer and a main chain that is an ethylene-propylene-diene copolymer. Such a copolymer in which a crystalline polypropylene macromonomer and an ethylene-propylene-diene copolymer have a physical bond is a dynamically crosslinked type composed of a matrix composed of crystalline polypropylene and a domain composed of a crosslinked rubber. In designing a thermoplastic elastomer (TPV) composition, it is an ideal material in that it has a strong matrix-domain interaction, and is expected to exhibit high performance even under microcrosslinking conditions. Moreover, since it has sufficient elastomeric properties derived from the skeleton structure, it is not necessary to increase the degree of cross-linking, so that it is expected to be used as a TPV composition with less coloring and resin deterioration than conventional products. It is also expected to be added as a compatibilizer to existing TPV compositions and contribute to improving its performance.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the thermoplastic elastomer excellent in heat resistance and mechanical characteristics with an economical manufacturing method.

Claims (17)

  Thermoplastic elastomer comprising a branched olefin copolymer having a main chain composed of a copolymer of ethylene, α-olefin and diene and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end It is a composition, Comprising: The thermoplastic elastomer composition whose diene content in the said principal chain is 0.1 mol% or more and 10 mol% or less.   The thermoplastic elastomer composition according to claim 1, wherein the diene is a diene having 4 to 20 carbon atoms.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the α-olefin content in the main chain is 5 mol% or more and 70 mol% or less.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the crystalline propylene polymer has an isotactic pentad fraction of 0.80 or more.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the crystalline propylene polymer has a syndiotactic pentad fraction of 0.60 or more.   The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the crystalline propylene polymer has a number average molecular weight of 50,000 or less.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein a glass transition point of the thermoplastic elastomer composition is -30 ° C or lower.   The thermoplastic elastomer composition according to any one of claims 1 to 7, wherein a density of the thermoplastic elastomer composition is 0.880 g / mL or less.   9. The thermoplastic elastomer composition according to claim 1, comprising a total of 30% by weight or less of the components derived from the crystalline propylene polymer and the crystalline propylene polymer. The thermoplastic elastomer composition as described.   The thermoplastic elastomer composition according to any one of claims 1 to 9, wherein the elongation at break of the thermoplastic elastomer composition is 500% or more.   The thermoplastic elastomer composition according to any one of claims 1 to 10, wherein the thermoplastic elastomer composition exhibits an elastic recovery rate of 70% or more upon recovery from 300% elongation. Branched structure olefin having a main chain composed of a copolymer of ethylene, α-olefin and diene, and a side chain derived from a crystalline propylene polymer having a vinyl group at one end and a number average molecular weight of 50,000 or less A method for producing a thermoplastic elastomer composition containing a copolymer, a mixing step of mixing the following components (a) to (d), and (d) in the main chain in the presence of a transition metal catalyst: The manufacturing method of a thermoplastic elastomer composition including the polymerization process of coordinatingly polymerizing the following (a)-(d) component so that diene content may be 0.1 mol% or more and 10 mol% or less.
(A) a crystalline propylene polymer having a vinyl group at one end, an isotactic pentad fraction of 0.80 or more, and a number average molecular weight of 50,000 or less (b) ethylene (c) at least 1 3 or more kinds of α-olefins (d) of at least one kind and 4 to 20 carbon atoms of a diene. Branched structure olefin having a main chain composed of a copolymer of ethylene, α-olefin and diene, and a side chain derived from a crystalline propylene polymer having a vinyl group at one end and a number average molecular weight of 50,000 or less A method for producing a thermoplastic elastomer composition containing a copolymer, wherein the following (a ′) to (d) components are mixed, and in the presence of a transition metal catalyst, (d And a polymerization step in which the following components (a ′) to (d) are coordinately polymerized so that the diene content is 0.1 mol% or more and 10 mol% or less.
(A ′) a crystalline propylene polymer having a vinyl group at one end, a syndiotactic pentad fraction of 0.60 or more, and a number average molecular weight of 50,000 or less (b) ethylene (c) at least 1 or more types of C3-C20 alpha olefin (d) At least 1 type of C4-C20 diene The method for producing a thermoplastic elastomer composition according to claim 12 or 13, wherein the transition metal catalyst is a complex represented by the following general formula (I).

(In General Formula (I), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, and T ¹ is a divalent group containing 1 to 30 atoms other than hydrogen atoms. R ² is a Lewis base. A heteroaryl group having 5 to 20 carbon atoms, wherein the heteroaryl group may have a substituent, M ¹ is a Group 4 metal of the periodic table, and X ¹ is monoanionic, dianion X represents the number of X ¹ groups and is an integer of 0 to 5. R ² and M ¹ may be bonded to each other to form a ring. (In the figure, a solid line represents a bond, a broken line represents an arbitrary bond, and an arrow represents a coordination bond.)   The heat according to claim 12 or 14, wherein in the mixing step, the mixing is performed so that the content of the component (a) is 30% by weight or less of the total amount of the components (a) to (d). A method for producing a plastic elastomer composition.   15. In the mixing step, mixing is performed so that the content of the component (a ′) is 30% by weight or less of the total amount of the components (a ′) to (d). A process for producing a thermoplastic elastomer composition.   In the production method, the thermoplastic elastomer composition is polymerized so that a total of the crystalline propylene polymer and components derived from the crystalline propylene polymer is 30% by weight or less. The manufacturing method of the thermoplastic-elastomer composition of any one of Claims 12-16.