JP6728844B2 - Thermoplastic elastomer composition - Google Patents

Description

The present invention is an elastomer containing a branched structure olefin-based copolymer having a main chain made of an ethylene/α-olefin copolymer 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 containing a composition and oil, and a molded article obtained by using the same.

The thermoplastic elastomer is an elastomer that is softened by heating to have fluidity and has rubber elasticity when cooled. The thermoplastic elastomer melts at the processing temperature during the molding process, and the molding process is easy by the well-known resin molding method, and after the molding process, at the temperature used as various materials (hereinafter, referred to as "usage temperature"), It is an industrially extremely useful material having the same physical properties as crosslinked rubber.

Heretofore, various multi-block copolymers such as block copolymers, especially triblock copolymers have been known as thermoplastic elastomers. In general, a block copolymer has a structure in which a "soft segment" having an amorphous or rubbery physical property and a "hard segment" in a crystalline state or a glass state at a use temperature of a typical thermoplastic elastomer are bonded. The polymer chains in the hard segment bond to each other at typical service temperatures and exhibit elastomeric properties. 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 has a thermoplastic behavior. Will be shown. 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, a lower temperature (eg 0°C or lower) or a higher temperature (eg 50°C or higher). ) Is expected, and heat resistance may be required. In that case, the thermal properties of the hard segment are important.

Well-known thermoplastic elastomer (TPE) compositions include styrene block copolymers (SBCs), for example, linear styrene-isoprene-styrene triblock copolymers and styrene-butadiene-styrene triblock copolymers. Examples include triblock copolymers. It is known that these copolymers have a relatively well-balanced block structure and, due to the relatively high Tg of the styrene segment, exhibit a relatively good balance between heat resistance and elastomericity. However, since these styrenic block copolymers are usually produced by sequential anionic polymerization or chemical coupling of linear diblock copolymers, the monomer species 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, resulting in poor process economy. Further, since the typical glass transition temperature of SBC is about 80 to 90° C., it has flowability again at a higher use temperature and has poor heat resistance, so that the use of these copolymers is limited.

In order to make up for these shortcomings of the prior art, it has been found to produce these block copolymers or thermoplastic elastomer compositions by insertion of olefin monomers with transition metal compounds, or by coordination polymerization, for process efficiency and raw material economy. From the viewpoint of the above, the improvement of physical properties by an olefin block copolymer, specifically, a propylene block copolymer is being investigated.

The propylene-based block copolymer has a higher Tm of the propylene segment than the Tg of the polystyrene segment of the styrene-based block copolymer, and thus has higher elastomeric properties than the styrene-based block copolymer, especially at high temperatures.
However, living polymerization catalysts are used when producing these propylene-based block copolymers. The living polymerization catalyst can theoretically obtain only one polymer chain from one catalyst molecule, has poor productivity, and its use is limited to a relatively small amount of high value-added fields.

Therefore, a method of producing a "block-like copolymer" by a method having higher productivity is being investigated. 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 with a monomer. Is being considered.
Patent Document 1 discloses an olefin-based thermoplastic elastomer composition having specific physical properties, which contains 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-based copolymer having an isotactic polypropylene segment in the side chain and a propylene-ethylene copolymer in the main chain.

In Patent Document 4, an ethylene/α-olefin copolymer having an isotactic polypropylene segment or a syndiotactic polypropylene segment having a number average molecular weight in a specific range in its side chain and a composition ratio in a specific range in its main chain is disclosed. A composition comprising a branched propylene-based copolymer having a polymer is disclosed. The thermoplastic elastomer composition having highly crystalline polypropylene in the side chain exhibits excellent elastomeric properties even when the side chain portion forming the hard segment is relatively low in content, and is particularly flexible but also has an excellent elastic recovery rate. ing. It is considered that this is because the highly crystalline polypropylene side chain exerts a particularly excellent action as a physical cross-linking point, and it is specific and excellent due to the combination of the highly crystalline polypropylene side chain and the ethylene terpolymer main chain. It is considered that this is due to the fact that the effects described above are exhibited.

A method using a shuttling material is known as an excellent method for producing an olefin block copolymer. As a specific olefin block copolymer, a continuous stir reactor connected in series is used to first create a soft segment composed of a copolymer of ethylene and α-olefin, and secondly to form a hard segment. Methods of making crystalline propylene and forming diblock copolymers are being investigated.

The olefin block copolymer can be blended with an oil or a filler to adjust flexibility and fluidity while maintaining good tensile strength, compression set and heat resistance.
In Patent Document 5, an elastomer composition obtained by oil-blending a diblock copolymer having an ethylene-propylene block and a crystalline propylene block is preferable to an oil-extended composition of ethylene-propylene-diene rubber (EPDM) and isotactic polypropylene. An example is disclosed in which a large compression set and A hardness are given and a large ultimate elongation is obtained.

Patent Document 6 discloses a composition for an olefin block copolymer having a soft segment and a hard segment, in which oil bleeding resistance is improved and tackiness is reduced by oil blending using a filler.

Special table 2001-527589 gazette Japanese Patent Publication No. 2001-525463 International Publication No. 2008/059969 International Publication No. 2013/061974 Special table 2013-506743 gazette Japanese Patent Publication No. 2013-532214

A thermoplastic elastomer composition exhibiting good heat resistance and mechanical strength may lack fluidity due to its generally high molecular weight and the like, so that sufficient moldability may not be obtained.
The composition described in Patent Document 4 is a thermoplastic elastomer composition exhibiting high mechanical properties, but has a problem that the productivity as a processed product is limited because of its high molecular weight and inferior molding processing speed.

It is generally known that an oil is blended with a thermoplastic elastomer composition to improve fluidity, but usually, fluidity and flexibility are improved as the amount of oil added is increased, but heat resistance is decreased on the other hand. That is, there was a trade-off relationship that the compression set at high temperature deteriorates. Further, in order to adjust the balance between fluidity and flexibility, a method of blending a crystalline polyolefin such as high-density polyethylene or isotactic polypropylene is known, but in general, as the amount of the crystalline polyolefin increases, heat resistance increases. It was also a problem that the sex was lowered.

In the oil-extended composition of the linear block copolymer having a diblock structure and the oil described in Patent Document 5, the compression set value at 70° C. cannot be said to be sufficient, and the compression heat resistance is not always sufficiently satisfied. I can't say that
The oil-extended composition described in Patent Document 6 has a relatively good compression set at 70° C., but does not mention high-temperature physical properties such as compression set at 100° C. or higher. Since the melting point of the olefin block copolymer is 125° C. or less and the main component is polyethylene, heat resistance cannot be expected under conditions exceeding 100° C., and the oil-extended composition has particularly poor heat resistance. is expected. In view of the above problems, it is an object of the present invention to provide a thermoplastic elastomer composition having both fluidity and heat resistance.

The present inventors have conducted extensive studies to solve the above problems, and as a result, found that an oil-extended composition of a specific branched structure olefin-based copolymer exhibits good fluidity and heat resistance, and the present invention Arrived
That is, the gist of the present invention is as follows.
[1] A thermoplastic elastomer composition containing the following components 1 and 2.
(Component 1) having a main chain of an ethylene/α-olefin copolymer and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end, and the α-olefin content in the main chain Is 70 mol% or less, an elastomer composition containing a branched structure olefin-based copolymer.
(Component 2) Oil [2] The thermoplastic elastomer composition according to [1], which further contains the following component 3 and/or component 4.
(Component 3) Filler (Component 4) Polyolefin [3] The thermoplastic elastomer according to [1] or [2], wherein the crystalline propylene polymer of Component 1 has an isotactic pentad fraction of 0.80 or more. Composition.
[4] The crystalline propylene polymer of component 1 has a number average molecular weight of 50,000 or less [1]
~ The thermoplastic elastomer composition according to any one of [3].
[5] In any one of [1] to [4], Component 1 contains the crystalline propylene polymer and components derived from the crystalline propylene polymer in a total amount of 30% by mass or more and 90% by mass or less. The thermoplastic elastomer composition described.
[6] Any one of [1] to [5] containing 50 to 200 parts by weight of oil, 0 to 200 parts by weight of filler, and 0 to 100 parts by weight of polyolefin with respect to 100 parts by weight of the elastomer composition. The thermoplastic elastomer composition described.
[7] The thermoplastic elastomer composition according to any one of [1] to [6], which has a compression set of 90% or less measured at 120° C. according to JIS K6262.
[8] The thermoplastic elastomer composition according to any one of [2] to [7], wherein the polyolefin is polyethylene, polypropylene, or a combination thereof.
[9] A molded product obtained by using the composition according to any one of [1] to [8].
[10] The molded product according to claim 9, which is selected from the group consisting of injection molded products, thermoformed products, and calendered products.

According to the present invention, it is possible to obtain a thermoplastic elastomer composition having both fluidity and heat resistance.

Hereinafter, the embodiments of the present invention will be described in more detail, but the description of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these, and the gist thereof Various modifications can be implemented within the range of.
The present invention is a thermoplastic elastomer composition containing the following components 1 and 2.
(Component 1) having a main chain of an ethylene/α-olefin copolymer and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end, and the α-olefin content in the main chain Is 70 mol% or less, an elastomer composition containing a branched structure olefin-based copolymer.
(Component 2) Oil Hereinafter, each component constituting the composition of the present invention will be described in more detail.

[(Component 1) Elastomer composition]
<Branched structure olefin-based copolymer>
The elastomer composition of the present invention contains a branched structure olefin-based copolymer as a constituent component.
The branched structure olefin-based copolymer is a crystalline propylene polymer whose main chain is a copolymer of ethylene and α-olefin and whose side chain contains a vinyl group at one end (hereinafter, referred to as “crystalline polypropylene macromolecule”). Sometimes referred to as "monomer").

The melting point (Tm) of the branched structure olefin-based copolymer used in the present invention is not particularly limited, but usually has a melting point (Tm) derived from a crystalline polypropylene macromonomer. These preferable values are similar to the preferable values for the crystalline polypropylene macromonomer, but may be different from the melting point (Tm) of the crystalline polypropylene macromonomer.
Usually, the branched structure olefin-based copolymer of the present invention exists as a mixture with unreacted raw materials in the polymerization product, so it is virtually impossible to isolate it and evaluate its molecular weight by itself. Is. Therefore, this molecular weight is evaluated as the molecular weight of the entire elastomer composition described later.

(Main chain: ethylene/α-olefin copolymer)
The main chain of the branched structure olefin-based copolymer of the present invention is an ethylene/α-olefin copolymer, that is, a copolymer of ethylene and α-olefin.
The copolymer of ethylene and α-olefin corresponds to the “soft segment” having an amorphous or rubbery physical property in the elastomer composition of the present invention. The backbone is usually low crystalline, preferably amorphous, to suit the "soft segment" domain characteristics.

The type of the ethylene/α-olefin copolymer used as the main chain is not particularly limited, but specifically, (b) ethylene and (c) at least one type having 3 to 20 carbon atoms. A copolymer obtained by copolymerizing with α-olefin, particularly from the viewpoint of process, economy and physical properties, (b) ethylene and (c-1) at least one α3 having from 8 to 3 carbon atoms. -Copolymers obtained by copolymerizing olefins are preferred.

The α-olefin used in the main chain is more preferably propylene, 1-butene, 1-hexene or 1-octene, further preferably propylene or 1-butene, and particularly preferably propylene. When the main chain is composed of ethylene and propylene, it is advantageous in terms of cost, and since the raw materials are both gases, the manufacturing process of the copolymerization reaction can be simplified and the productivity can be improved.

The content of the α-olefin contained in the ethylene/α-olefin copolymer, that is, the content of the α-olefin in the main chain is 70 mol% or less, preferably 60 mol% or less, and more preferably 50 mol%. It is as follows. 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 decreased, and the branched structure olefin is formed. It may be difficult to form physical cross-linking points between the copolymer chains. On the other hand, if the amount is less than the lower limit, the flexibility becomes poor and the properties required as an elastomer may not be obtained.

The main chain may contain a copolymerization component other than ethylene/α-olefin within a range not impairing the effects of the present invention. Diene is mentioned as a concrete copolymerization component.
The diene used in the main chain is not particularly limited as long as it has two or more double bonds in the monomer molecule, and may be a conjugated diene or a non-conjugated diene. It may have a straight chain or a branched chain, and may have a cyclic structure in the molecule.

The number of carbon atoms of the diene is not particularly limited, but it is usually a diene having 4 to 20 carbon atoms, and preferably a diene having 8 to 20 carbon atoms.
As a preferable diene, a diene having a structure that is easily copolymerized (for example, a terminal vinyl group or norbornene skeleton) is preferable in terms of reactivity. In addition, one having a high reaction selectivity of the double bond portion in the diene, that is, of the two double bonds in the diene, one double bond is consumed by the copolymerization, and one double bond is added to the polymer. What remains as a double bond is preferable because it does not crosslink in 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 and cyclo. Hexadiene and 4-vinylcyclohexene are mentioned. Particularly preferred dienes are 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinylcyclohexene.

When the main chain contains a diene, the content of the diene in the main chain is not particularly limited, but is usually lower than the content of the α-olefin in the main chain, usually 0.1 mol% or more, 10 or less.
It is at most mol%, preferably at most 5 mol%, more preferably at most 1 mol%, and even more preferably at most 0.5 mol%. When the diene content in the main chain exceeds the upper limit, when the branched structure olefin-based 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, A coarse gel may be generated without being finely dispersed in the matrix.

When the main chain contains a diene, the sum of the α-olefin content in the main chain and the diene content in the main chain is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, It is usually 70 mol% or less, preferably 60 mol% or less.
The glass transition point (Tg) of the ethylene/α-olefin copolymer used as the main chain in the present invention is not particularly limited, but the glass transition point (Tg) is usually -30°C or lower. , Preferably -50°C or lower.

The weight average molecular weight (Mw) of the ethylene/α-olefin copolymer used as the main chain in the present invention is not particularly limited, but is preferably 300,000 or more, more preferably 500,000 or more, and usually It is 5,000,000 or less, preferably 3,000,000 or less. Since the branched structure olefin-based 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, but the same catalyst system results in crystallinity. Evaluate by discounting the influence of side chains from the molecular weight of ethylene/α-olefin copolymers that do not contain side chains derived from polypropylene macromonomers and the actual molecular weight of branched olefin copolymers. You can When the weight average molecular weight (Mw) of the ethylene/α-olefin copolymer used as the main chain is at least the above lower limit value, the crystalline polypropylene macromonomer corresponding to the side chain is sufficiently introduced into the main chain to exhibit good elastomer physical properties. If the content is less than the above upper limit, it becomes easy to control the melt fluidity by oil extension, and problems such as poor stirring during production hardly occur and good productivity is exhibited.
The polymerization mode of the ethylene/α-olefin copolymer used as the main chain in the present invention is not particularly limited as long as the physical properties of the elastomer of the present invention can be obtained, but usually the α-olefin is randomly distributed in the main chain. It is an ethylene/α-olefin copolymer in a copolymerized form.

(Side chain derived from crystalline polypropylene macromonomer)
The side chain of the branched structure olefin-based copolymer of the present invention is derived from a crystalline propylene polymer having a vinyl group at one end, and is derived from a so-called crystalline polypropylene macromonomer. In the elastomer composition of the present invention, the side chain functions as a "hard segment" in a crystalline state or a glass state, and exhibits a property as an elastomer by being bonded to the main chain portion which is a "soft segment". I think it will be. Specifically, the side chains crystallize intermolecularly as "hard segments" and cross-link the main chain portions which are "soft segments", thereby giving the composition properties as an elastomer. The crystals of polypropylene are particularly rigid among other crystalline polyolefins, and therefore, the side chains derived from the crystalline polypropylene macromonomer are considered to have particularly high performance as a hard segment. Further, 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-based hard segments.

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

The crystalline polypropylene macromonomer usually has a vinyl group at one end, but in the crystalline polypropylene macromonomer, a molecule having no vinyl group at either end or both ends having a vinyl group. And a molecule having a vinylidene group at at least one end. Preferably, the macromonomer molecule has a vinyl group at one end and an alkyl group at the other end.

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 t-vinyl% is less than 50%, of the added crystalline polypropylene macromonomer, the proportion of the side chain incorporated into the branched structure olefin-based copolymer of the present invention is small, and the performance of the copolymer as an elastomer is unsatisfactory. May be sufficient. The ratio (t-vinyl%) of macromonomer molecules having a vinyl group at one end represents the ratio of the number of molecules having a vinyl group at the end, out of all macromonomer molecules, and is specifically calculated as follows. To be done.

(T-vinyl %)=[Mn(GPC)]/[Mn(NMR)]×100
Here, [Mn(GPC)] is the number average molecular weight of the macromonomer measured by GPC, and [Mn(NMR)] is the vinyl group and the other end of all the macromonomer molecules. Is a number average molecular weight of the macromonomer calculated from the total number of protons on the alkyl carbon (sp ³ carbon) other than the vinyl group, which is determined by NMR measurement.

In order to satisfy the above characteristics, the crystalline polypropylene macromonomer is produced using an appropriate catalyst and polymerization conditions such as the production method described below.
The crystalline polypropylene macromonomer may be a branched crystalline polypropylene macromonomer having a crystalline polypropylene side chain as long as it does not impair rigidity and heat resistance.

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 stereoregularity of polypropylene. Pentad indicates the continuity of relative arrangement of adjacent side chain methyl groups of polypropylene, and the higher the value, the higher the stereoregularity. The isotactic pentad fraction (mmmm) is the ratio of the propylene unit at the center of the chain in which five propylene monomer units are continuously meso-bonded to the total propylene unit, expressed as a percentage. The syndiotactic pentad fraction (rrrr) is the ratio of the propylene unit at the center of the chain in which five propylene monomer units are continuously racemic-bonded to all propylene units, expressed as a percentage. Pentads are usually determined by ¹³ C-NMR. In addition, specifically, it is obtained by the method described in the literature (Chem. Rev. 2000, 100, 1253-1345). The structure of the crystalline polypropylene macromonomer used in the present invention preferably has a high isotactic pentad fraction (mmmm) or a high syndiotactic pentad fraction (rrrr). These are "hard segments" that form stronger crystals with a high degree of crystallinity between the olefinic copolymers having a branched structure, and this acts as a stronger cross-linking point, resulting in excellent elastomer performance. This is because it is considered to give.

A crystalline polypropylene macromonomer having a high isotactic pentad fraction (hereinafter sometimes referred to as “isotactic polypropylene macromonomer”) means that the isotactic pentad fraction (mmmm) is usually 0.80. Or more, preferably 0.90 or more. As the isotactic pentad fraction increases, the melting point rises and the heat resistance is further improved, which is preferable. 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 calculated upper limit.

A polypropylene macromonomer having a high syndiotactic pentad fraction (hereinafter sometimes referred to as "syndiotactic polypropylene macromonomer") has a syndiotactic pentad fraction (rrrr) of usually 0.60 or more. It is preferably 0.70 or more, more preferably 0.80 or more, 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 calculated upper limit.

As a constituent component of the side chain of the branched structure olefin-based copolymer of the present invention, an α-olefin other than ethylene or propylene, or a component derived from a diene may be contained. Some amount of hetero-bonds that can be introduced in the process of polymerizing polypropylene and some amount of comonomers for compensating the solubility during polymerization are acceptable as long as the rigidity of the side chain and the heat resistance are not significantly impaired. From the viewpoint of maintaining the rigidity and heat resistance of the side chain, the side chain is preferably derived from a propylene homopolymer.

The melting point (Tm) of the crystalline polypropylene macromonomer used in the present invention is usually 60°C or higher, preferably 80°C or higher, more preferably 100°C or higher, further preferably 120°C or higher, more preferably 150°C or higher, usually It is 165°C or lower, preferably 160°C or lower. When the melting point is above the lower limit, the heat resistance of the thermoplastic composition is improved, and when it is below the upper limit, a sufficient amount of crystalline polypropylene macromonomer is introduced into the main chain as a side chain. 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 act 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-based copolymer, its performance as an elastomer Is not expected. The crystallization temperature (Tc) of the crystalline polypropylene macromonomer is not particularly limited, but is generally lower than the melting point and depends on the crystallization rate and the cooling rate. The crystallization temperature as well as the melting point can be defined by differential thermal analysis (DSC).

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 desired physical and mechanical properties.
The number average molecular weight of the crystalline polypropylene macromonomer is usually 50,000 or less, preferably 30,000 or less. The number average molecular weight (Mn) of the macromonomer is usually 1,000 or more, preferably 3,000 or more, more preferably 10,000 or more. When the number average molecular weight of the crystalline polypropylene macromonomer exceeds the upper limit, the number of molecules of the macromonomer with respect to the weight of the macromonomer used in the polymerization reaction decreases, and as a result, it is introduced into the branched structure olefin-based copolymer. The number of side chains is reduced. In order for the elastomer composition of the present invention to exhibit the function as an elastomer, at least two side chains per one main chain of the branched structure olefinic copolymer molecule of the present invention, that is, two or more side chains are used. Although a physical cross-linking point is required, the number of side chains is reduced, so that a sufficient number of physical cross-linking points in the branched structure olefin-based copolymer may not be obtained, which impairs the elastomer performance. Sometimes. Further, 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 growth of physical crosslink points between polymer chains is not promoted. Elastomer performance may be reduced.

The number average molecular weight of the crystalline polypropylene macromonomer is as described above, the number average molecular weight of the macromonomer measured by GPC ([Mn(GPC)]) and the number average molecular weight quantified by ¹ H-NMR spectrum ([Mn (NMR)], but the "number average molecular weight of crystalline polypropylene macromonomer" is usually the value ([Mn(GPC)]) obtained from GPC, and in the present invention, the number average molecular weight of When the values are different, the number average molecular weight by GPC ([Mn(GPC)]) is taken as the number average molecular weight, and [Mn(NMR)] is the ratio (t of the molecules having a vinyl group at one end described above). -Vinyl%).

The molecular weight distribution of the crystalline polypropylene macromonomer used in the present invention is not particularly limited, but it is preferable that the molecular weight distribution of the side chain is as narrow as possible in order to enable precise physical property control by the molecular weight of the side chain. The crystalline polypropylene macromonomer used in the present invention has a molecular weight distribution of Mw/Mn of usually 1 or more and 6 or less, preferably 3 or less.
The content of the side chain derived from the crystalline propylene macromonomer contained in the branched structure olefin-based copolymer of the present invention is not particularly limited. It is usually 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, based on all the raw materials and all the monomers constituting the coalescence. It is preferably 75% by mass or less. If this ratio is less than the lower limit, the number of copolymer chains substantially containing side chains is small, and physical crosslinking between polymer chains tends to be difficult to form. Further, if the upper limit is exceeded, the flexibility of the entire composition tends to be poor, and the composition may not be suitable for the properties required as a thermoplastic elastomer.

The crystalline polypropylene macromonomer used in the present invention, specifically, the method for producing the isotactic polypropylene macromonomer or the syndiotactic polypropylene macromonomer is not particularly limited, and conventionally known macromonomers. The production method of (1) can be appropriately used, and a method capable of efficiently producing a highly crystalline polypropylene macromonomer is preferable. More specifically, a method that is produced by coordination polymerization of propylene using a transition metal compound and has a high proportion of termination terminals of polymerization to form vinyl groups is preferable from an economical viewpoint.

For example, as a method for producing the isotactic polypropylene macromonomer, a stereorigid C2 symmetric bridged metallocene catalyst is used, and by utilizing the fact that β-methyl group elimination reaction occurs frequently by polymerizing propylene at high temperature, A method of introducing a vinyl group at the terminal (for example, Japanese Patent Publication No. 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 for producing while maintaining high stereoregularity by increasing the frequency of β-methyl elimination reaction at a relatively low temperature (for example, JP-A Nos. 11-349634 and 2009-299045), isotactic Copolymerization of vinyl comonomers with easily removable functional groups such as vinyl chloride in propylene by structure-selective metallocene catalyst, and this comonomer causes β-functional group elimination at the same time as insertion and selectively produces macromonomers with terminal vinyl groups. The method of production (Gaynor, SG Macromolecules 2003, 36, 4692-4698) and the propylene polymerization catalyst in which the 2,1-insertion of propylene takes precedence (eg, as represented by pyridyldiimine iron (II) complexes). Periodic transition metal complex), and a terminal vinyl group is introduced through β-hydrogen elimination without undergoing a relatively difficult β-methyl group elimination process (Brookhart, M. et al. Macromolecules 1999). , 32, 2120) and the like.

By using a complex having a heterocyclic group at a specific site among them, 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 2009- 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 an uncrosslinked metallocene catalyst having a very bulky substituent (Resconi, L. et. al. J. Am. Chem. Soc. 1992, 114, 1025.), a method of polymerizing propylene at high temperature using a stereorigid Cs symmetric bridged metallocene catalyst (JP-A No. 2001-525461), a syndiotactic selective metallocene catalyst in propylene, a function such as vinyl chloride that is easily eliminated. A method for copolymerizing a vinyl comonomer having a group and causing β functional group elimination upon insertion of the vinyl comonomer to selectively produce a macromonomer having a terminal vinyl group (Kaminsky, W. et. al. Macromol. Chem. Phys. 2010, 211, 1472-1481), in which a bis(phenoxyimine) titanium complex having a specific substituent is vinyl-terminated at the terminal of syndiotactic polypropylene by β-hydrogen elimination from the 2,1-insertion of propylene. A method in which a group is selectively introduced (such as WO 03/025025, or Cherian, AE et al, Macromolecules 2005, 38, 6268) and the like can be mentioned.

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 the 2,1-insertion of propylene causes syndiotactic A method of selectively introducing a vinyl group at the terminal of tic polypropylene is preferable.
Particularly preferably, during the production of the crystalline polypropylene macromonomer, it is possible to selectively introduce a vinyl group at the terminal efficiently at a lower temperature, and the macromonomer can be produced at a temperature close to the subsequent polymerization temperature of the copolymer. From the above advantage, it is preferable to use the catalyst described in JP-A-2009-299045, and more preferable to use the method of producing a transition metal compound represented by the following general formula (II).

In the general formula (II), R ¹¹ and R ¹² each independently represent a heterocyclic group containing 4 to 16 carbon atoms, containing nitrogen, oxygen, or sulfur. Further, R ¹³ and R ¹⁴ are each independently an aryl which may contain at least one hetero atom selected from halogen having 6 to 16 carbon atoms, silicon, oxygen, sulfur, nitrogen, boron, and phosphorus. Represents a group or a heterocyclic group having 6 to 16 carbon atoms, containing nitrogen, oxygen, or sulfur. Further, X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Represents a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group.

The heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, Alternatively, it is a substituted 2-furfuryl group, more preferably a substituted 2-furyl group.
By introducing a substituent of appropriate size on the heterocyclic group, the relative position between the heterocycle and the coordination field on the transition metal and the growing polymer chain can be made appropriate, and the vinyl group at the terminal can be adjusted. It is possible to obtain a crystalline polypropylene macromonomer in which a group is highly selectively introduced.

In addition, the substituted 2-furyl group, the substituted 2-thienyl group, and the substituted 2-furfuryl group have a methyl group, an ethyl group, a propyl group, or another alkyl group having 1 to 6 carbon atoms. , A halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.

Furthermore, as R ¹¹ and R ¹² , a 2-(5-methyl)-furyl group is particularly preferable. Further, it is preferable that R ¹¹ and R ¹² are the same as each other.
The above R ¹³ and R ¹⁴ are aryl groups having 6 to 16 carbon atoms, which may contain at least one hetero element selected from halogen, silicon, oxygen, sulfur, nitrogen, boron, and phosphorus, or 6 to 6 carbon atoms. 16 is a heterocyclic group containing nitrogen, oxygen, or sulfur, and in particular, by making R ¹³ and R ¹⁴ more bulky, a crystalline polypropylene macromonomer having higher stereoregularity and less heterogeneous bonds. Can be obtained.

Therefore, R ¹³ and R ¹⁴ are one or more hydrocarbon groups having 1 to 6 carbon atoms and silicon-containing hydrocarbons having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. Group, an aryl group having a halogen-containing hydrocarbon group having 1 to 6 carbon atoms as a substituent, and specific examples of such R ¹³ and R ¹⁴ include a phenyl group, a 4-isopropylphenyl group, and a 4-t- group. A butylphenyl group, a 2,3-dimethylphenyl group, a 3,5-di-t-butylphenyl group, a 4-chlorophenyl group, a 4-trimethylsilylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Further, R ¹³ and R ¹⁴ are more preferably one or more hydrocarbon groups having 1 to 6 carbon atoms and silicon-containing hydrocarbon groups having 1 to 6 carbon atoms in the range of 6 to 16 carbon atoms. , A phenyl group having a halogen-containing hydrocarbon group having 1 to 6 carbon atoms as a substituent. Furthermore, the position to be substituted is preferably the 4-position on the phenyl group. Specific examples of R ¹³ and R ¹⁴ are 4-isopropylphenyl group, 4-t-butylphenyl group, 4-biphenylyl group, 4-chlorophenyl group, and 4-trimethylsilylphenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same as each other.

In formula (II), X ¹¹ and Y ¹¹ are auxiliary ligands. Therefore, as long as this object is achieved, the types of X ¹¹ and Y ¹¹ are not limited, and each independently, hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. An alkoxy group, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

In the general formula (II), Q ¹¹ is a silylene which may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. A group or a germylene group is shown. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc.; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene. An alkylsilylene group such as (n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, an (alkyl)(aryl)silylene group such as methyl(phenyl)silylene; an arylsilylene group such as diphenylsilylene; Alkyloligosilylene group such as tetramethyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl) (aryl) Germylene group; arylgermylene group and the like can be mentioned. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

The transition metal compound represented by the general formula (II) is usually used in combination with a cocatalyst described later. Preferably, an organoaluminum oxy compound, an ionic compound capable of reacting with a catalyst precursor and converting it into a cation, a Lewis acid, an ion-exchange layered silicate or the like is used as a cocatalyst, and particularly preferably an organic compound. Aluminum oxy compounds and ion-exchange layered silicates are used. Further, in the above combination, an organoaluminum compound may be further used in combination.

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 coordination polymerization of propylene from the economical viewpoint. The polymerization conditions are not particularly limited as long as the intended product can be obtained, and solution polymerization, slurry polymerization, liquid phase solventless polymerization (bulk polymerization) that does not substantially use a solvent, gas phase polymerization, melt polymerization, etc. can be used. Yes, continuous polymerization, batch polymerization, and so-called multi-stage polymerization may be adopted.

The polymerization temperature, the polymerization pressure and the polymerization time are not particularly limited, but usually can be appropriately set in consideration of the productivity and the selectivity of the terminal vinyl group.
The polymerization temperature is usually 0° C. or higher, preferably 30° C. or higher, more preferably 50° C. or higher, particularly preferably 70° C. or higher, and usually 150° C. or lower, preferably 100° C. or lower. The polymerization pressure is usually 0.01 MPa or higher, preferably 0.05 MPa or higher, more preferably 0.1 MPa or higher, and usually 100 MPa or lower, preferably 20 MPa or lower, more preferably 5 MPa or lower. This is because, when produced by this method, the terminal of the crystalline polypropylene macromonomer molecule is usually an alkyl group at the starting end of the polymerization reaction and a vinyl group at the ending end of the polymerization reaction with a high probability. In this case, the possibility that both ends of the macromonomer molecule will be vinyl groups is usually extremely low.

<Other ingredients>
The elastomer composition of the present invention usually contains the following components (B) and (C) in addition to the above-mentioned branched structure olefin-based copolymer (hereinafter sometimes referred to as “(A) component”). It is included (hereinafter, may be referred to as “(B) component” and “(C) component”, respectively).
(B) Copolymer of ethylene and α-olefin (C) Crystalline polypropylene macromonomer Component (B) is usually an ethylene/α-olefin copolymer produced in the synthesis reaction of the above-mentioned copolymer (A) component. It corresponds to a polymer in which the macromonomer is not incorporated into and only the main chain component is formed.

The component (C) is usually a reaction raw material during the production of the component (A), and specifically corresponds to an unreacted macromonomer that has not been incorporated in the synthesis reaction of the copolymer (A). The macromonomer added to the reaction system of the synthesis reaction of the component (A) is usually incorporated as a side chain of the component (A) or contained in the thermoplastic elastomer composition of the present invention as the component (C).

The weight ratio of the macromonomer incorporated into the component (A) and the component (C) is not particularly limited and is appropriately adjusted so as to satisfy the desired physical properties.
The proportions of the above-mentioned components (A), (B) and (C) contained in the composition of the present invention are not particularly limited, but may be arbitrarily adjusted so as to satisfy the desired physical properties. The component (B) and the component (C) are preferably contained in a small amount, and more preferably the composition of the present invention is composed of the component (A) only.

The elastomer composition of the present invention containing the above components (A) to (C) may be obtained as a result of a copolymerization reaction during the production of the component (A) as described above. The components) may be independently synthesized and mixed, but those obtained as a result of the copolymerization reaction during the production of the component (A) are preferable from the viewpoint of ease of production.
The crystalline polypropylene macromonomer contained in the elastomer composition of the present invention and the component derived from the crystalline polypropylene macromonomer, that is, the crystalline polypropylene introduced into the component (C) and the component (A) as a side chain. The total content of the components derived from the macromonomer is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more. On the other hand, this content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. When the amount exceeds the upper limit, the flexibility of the entire composition tends to be poor, and the composition may not be suitable for the properties required as a thermoplastic elastomer. On the other hand, if the amount is less than the above lower limit, the number of copolymer chains containing side chains is substantially reduced, and physical crosslinking between polymer chains tends to be difficult to form.

(2) Physical Properties Since the elastomer composition of the present invention is evaluated as a physical property value as a mixture of the component (A), the component (B), and the component (C) of the above-mentioned component (1), the component (A) is usually used. Which has a glass transition point derived from a copolymer of ethylene and α-olefin, which is the main chain of (A) and the component (B) itself, and which is the side chain of the component (A) and the component (C) itself. It has a melting point derived from some crystalline polypropylene macromonomer.

The glass transition point (Tg) of the elastomer 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 (B), it usually has a glass transition point in the same range as that of the component (B). The glass transition points may not match due to the composition ratio and the like. Further, since the melting point of the composition of the present invention depends on the melting point of the component (C), it usually has a melting point in the same range as the preferable value of the melting point of the crystalline polypropylene macromonomer. The melting point of the crystalline polypropylene macromonomer may not coincide with the melting point of the crystalline polypropylene macromonomer depending on the composition ratio in the elastomer composition.

The molecular weight of the elastomer composition of the present invention is not particularly limited, but the weight average molecular weight (Mw) is measured by GPC and is preferably 300,000 or more, more preferably 500,000 or more.
When the composition has a molecular weight within the above range, the melt flowability of the composition is improved, the moldability is improved, and an easily processable elastomer can be obtained.

The physical properties of the elastomer composition of the present invention as an elastomer are described, for example, in Proceedings of the National Academia of Sciences (2006) vol. 103(42) pp. It can be determined by the method described in Experimental Section 15327, or Macromolecules 2008, 41, 9548-9555.

<Method for producing elastomer composition>
The method for producing the elastomer composition of the present invention is not particularly limited as long as the intended composition can be obtained, but the following methods can be mentioned.
(Method 1) A crystalline polypropylene macromonomer, ethylene, and α-olefin are mixed and polymerized to produce an elastomer composition.
(Method 2) Each of the components (A) to (C) is synthesized and mixed to produce an elastomer composition.
Method 1 is more advantageous in manufacturing efficiency. The method 1 will be described below.

(material)
As the raw material, the following components (a) to (c) are preferable.
(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) α-Olefin The above (a) may be changed to the following (a′).

(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) component, The components (c) and (c) correspond to raw materials forming the main chain portion of the branched structure olefin-based copolymer.
(B) Ethylene is not particularly limited, and refined ones and those obtained from various petrochemical plants are used, but purified ethylene is preferable in terms of quality.

The component (c) is usually 3 to 20·BR> α-olefin, but from the viewpoint of process, economy and physical properties, (c-1) at least one α-olefin having 3 to 8 carbon atoms. Is preferred.
Two or more types of component (c) may be used in combination.
As the component (a), one type may be used alone, or two or more types having different isotactic pentad fractions and number average molecular weights may be used in combination.

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.
(Mixing of raw materials)
The step of mixing the crystalline polypropylene macromonomer, ethylene, and α-olefin is not particularly limited, and does not interfere with the step of coordination polymerizing the above-mentioned components in the presence of a transition metal catalyst in the next step. As long as it is possible, any mixing method can be selected.

Further, the order of mixing is not particularly limited, and the above-mentioned respective components may be charged all at once and mixed, or may be additionally added and mixed during the polymerization reaction. The amount of α-olefin used is appropriately adjusted according to the α-olefin content in the main chain of the branched structure olefin-based copolymer and the transition metal catalyst used in the polymerization step.
It is preferable that, after the above mixing, the crystalline polypropylene macromonomer is dissolved or melted in the solvent used at the time of polymerization to be in a uniform state at the start of polymerization.

The content of the crystalline polypropylene macromonomer in the total amount of the crystalline polypropylene macromonomer, ethylene, and α-olefin is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, and usually 70% by mass or less. , Preferably 60% by mass or less.
The content of ethylene in the total amount of the crystalline polypropylene macromonomer, ethylene, and α-olefin is not particularly limited, but is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, It is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more.

The content of the α-olefin in the total amount of the crystalline polypropylene macromonomer, ethylene, and the α-olefin is not particularly limited, but is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. It is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.
The charging ratio of the crystalline polypropylene macromonomer, ethylene, and the α-olefin is not particularly limited, but usually, the ratio of the crystalline polypropylene macromonomer, ethylene, and the α-olefin in the elastomer composition described later (to the polymer) A large amount of ethylene is added to the ratio including the amount taken in). When the α-olefin is a gas, a large amount of α-olefin is also added. This is because the gas raw material tends to be lost without being incorporated into the branched structure olefin-based copolymer.

(Polymerization process)
(I) Transition metal catalyst A crystalline polypropylene macromonomer, ethylene, and an α-olefin are usually polymerized in the presence of a transition metal catalyst. As used herein, transition metal catalysts also include transition metal catalyst precursors. Examples of the transition metal catalyst include those represented by the following general formula (I).

In the above general formula (I), M is at least one metal atom selected from titanium, zirconium and hafnium. R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a teloatom-containing alkyl group, a heteroatom-containing cycloalkyl group, an aryl group, and a silyl group. It is at least one selected from the group, and these groups may further have a substituent. In R ^{1 to} R ⁵ , adjacent ones may be bonded to each other to form a condensed ring, and at least one of them may form a divalent crosslinkable group with Z. Further, X is at least one selected from a monoanionic ligand, a dianionic ligand, and a neutral ligand, and m represents the number of X ¹ and is an integer of 0 to 5. ..

Z is at least one atom selected from nitrogen, phosphorus, oxygen and sulfur, or a substituent containing the atom, and is between M and at least one atom selected from nitrogen, phosphorus, oxygen and sulfur. Represents a covalent bond.
M represents at least one metal atom selected from titanium, zirconium and hafnium, preferably titanium or hafnium, and more preferably titanium.

R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a hetero atom-containing alkyl group, a hetero atom-containing cycloalkyl group, an aryl group, and a silyl group. And at least one selected from the group consisting of hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group and a silyl group.
Here, the hetero atom means an atom other than a hydrogen atom and a carbon atom, and is specifically at least one atom selected from oxygen, nitrogen, phosphorus, silicon, germanium, sulfur and halogen.

These groups may further have a substituent. Specific examples of the substituent include a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a silyl group and the like.
Two adjacent R ^{1 to} R ⁵ may combine with each other to form a condensed ring. Specifically, as the condensed ring, a substituted indenyl group, a substituted azulenyl group, a substituted fluorenyl group or the like containing a conjugated 5-membered ring (cyclopentadienyl ring) of the formula (I) may be formed.

At least one selected from R ^{1 to} R ⁵ may form a divalent crosslinking group with Z. Preferably, ^one of R ^{1 to} R ⁵ forms a divalent crosslinking group with Z.
Specific examples of R ^{1 to} R ⁵ in the case of forming the cross-linking group include an alkylene group having 1 to 20 carbon atoms, a silylene group, a germylene group and the like, and preferably a substituent having 1 to 20 carbon atoms. It is a silylene group.

X is at least one selected from a monoanionic ligand, a dianionic ligand, and a neutral ligand. Specifically, examples of the monoanionic ligand include hydrogen, halogen, a hydrocarbon group, and a substituent-containing hetero group. Examples of the dianionic ligand include diols, diamines, and divalent derivatives of conjugated dienes. Examples of neutral ligands include neutral π-bonded conjugated dienes. Of these, preferred as X is a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

m represents the number of X and is an integer of 0 to 5, preferably 1 or 2, and more preferably 2. When m is 2 or more, the plurality of X may be the same or different, but the same is preferable.
Z is at least one atom selected from nitrogen, phosphorus, oxygen and sulfur or a substituent containing the atom, wherein at least one atom selected from nitrogen, phosphorus, oxygen and sulfur is M. Represents what forms a covalent bond between. Of the at least one atom selected from nitrogen, phosphorus, oxygen and sulfur, nitrogen or oxygen is preferable.

Specific examples of Z include a substituted amino group having 1 to 30 carbon atoms, a substituted amide group having 1 to 30 carbon atoms, a substituted imide group having 1 to 30 carbon atoms, a substituted phosphine imide group, an oxygen atom, and 1 to 30 carbon atoms. Examples thereof include an alkoxy group, an aryloxy group having 5 to 30 carbon atoms, a sulfur atom, a substituted sulfide group and a substituted sulfone group, and preferably an amino group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and carbon. It is an aryloxy group of several 5 to 30. These groups may further have a substituent.
Preferred transition metal catalysts of the general formula (I) include transition metal catalysts of the following general formula (I-1).

In the general formula (I-1), M, R ^{1 to} R ⁵ , X and Z have the same definitions as in the above general formula (I). R ⁵ forms a divalent crosslinking group with Z.
More preferable transition metal catalysts of the general formula (I) include transition metal catalysts of the following general formula (I-2).

In the above formula (I-2), M, R ^{1 to} R ⁵ , and X have the same definitions as in the above general formula (I).
R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a hetero atom-containing alkyl group, a hetero atom-containing cycloalkyl group, an aryl group or a silyl group, preferably a silyl group, and these groups are further It may have a substituent, and is preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group.

Specific examples of the transition metal catalyst represented by the above general formula (I-2) include the following.
Dimethylsilyl (cyclododecylamide) (tetramethylcyclopentadienyl) dichloride, dimethylsilyl (cyclododecylamide) (tetramethylcyclopentadienyl) dimethyl, dimethylsilyl (t-butylamide) (tetramethylcyclopentadienyl) titanium Dichloride, dimethylsilyl(t-butylamide)(tetramethylcyclopentadienyl)titanium dimethyl, dimethylsilyl(t-butylamido)(tetramethylcyclopentadienyl)titanium(II) 1,4-diphenyl-1,3-butadiene , Dimethylsilyl(t-butylamido)(2,3,5-trimethylcyclopentadienyl)titanium dichloride, dimethylsilyl(t-butylamido)(3-n-butylcyclopentadienyl)titanium dichloride, dimethylsilyl(t- Butyramide) (3-t-butylcyclopentadienyl) dichloride, dimethylsilyl (t-butylamido) (2-methylindenyl) titanium dichloride, dimethylsilyl (t-butylamido) (2,3-dimethylindenyl) titanium dichloride , Dimethylsilyl(t-butylamido)(2-methyl-4-indenyl)titanium dichloride, dimethylsilyl(t-butylamido)(3-phenylcyclopentadienyl)titanium dichloride, dimethylsilyl(t-butylamide) (3,4 -Diphenylcyclopentadienyl)dichloride, dimethylsilyl(t-butylamido)(cyclopenta[l]phenanthren-2-yl)titanium dichloride, dimethylsilyl(t-butylamido)(3-phenylindenyl)titanium dichloride, dimethylsilyl( t-Butylamido)(3-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)titanium dichloride, dimethylsilyl(t-butylamido)(fluoren-9-yl)titanium dichloride, dimethylsilyl( t-Butylamido)(tetrahydrofluoren-9-yl)titanium dichloride, dimethylsilyl(t-butylamido)(octahydrofluoren-9-yl)titanium dichloride, dimethylsilyl(t-butylamide)(2,7-di-t- Butylfluoren-9-yl)titanium dichloride, dimethylsilyl(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methyl Isoindole)-(3H)-inden-2-yl)dichloride, dimethylsilyl(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2',3']( 1-methylisoindole)-(3H)-inden-2-yl)dichloride, dimethylsilyl(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindole) Indole)-(3H)-inden-2-yl)titanium dichloride, dimethylsilyl(t-butylamido)(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)titanium dichloride, dimethylsilyl (T-Butylamido)(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)titanium dichloride.

In the above-mentioned transition metal catalyst of the general formula (I), a more preferable embodiment is a transition metal catalyst of the following general formula (I-3).

Examples of transition metal catalysts of formula (I-3) suitable for use in the present invention include: M, R ^{1 to} R ⁵ , and X have the same definitions as in the above general formula (I).
R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a hetero atom-containing alkyl group, a hetero atom-containing cycloalkyl group, an aryl group, and a silyl group. It is at least one selected from the group, and these groups may further have a substituent. Two adjacent ones of R ^{1 to} R ⁵ may be bonded to each other to form a condensed ring.

Specific examples of the transition metal catalyst represented by the above general formula (I-3) include the following.
Dimethylsilyl(cyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl)(3-t-butyl- 5-Methyl 2-phenoxy)titanium dichloride, dimethylsilyl(fluoren-9-yl)(3-t-butyl-5-methyl2-phenoxy)titanium dichloride, dimethylsilyl(2,7-di-t-butylfluorene-) 9-yl)(3-t-butyl-5-methyl-2-phenoxy)titanium dichloride.

In another aspect of the more preferred transition metal catalyst of the general formula (I), specifically, at least one selected from R ^{1 to} R ⁵ does not form a divalent crosslinking group with Z. , Including:
Cyclopentadienyl(2,6-diisopropylphenoxy)titanium dichloride, pentamethylcyclopentadienyl(2,6-diisopropylphenoxy)titanium dichloride, tert-butylcyclopentadienyl(2,6-diisopropylphenoxy)titanium dichloride, Cyclopentadienyl(2,6-diphenylphenoxy)titanium dichloride, pentamethylcyclopentadienyl(2,6-diphenylphenoxy)titanium dichloride, tert-butylcyclopentadienyl(2,6-diphenylphenoxy)titanium dichloride, Cyclopentadienyl (2,2,4,4-tetramethylpentane-3-ylideneamino)titanium dichloride, pentamethylcyclopentadienyl (2,2,4,4-tetramethylpentane-3-ylideneamino)titanium dichloride, tert-Butylcyclopentadienyl(2,2,4,4-tetramethylpentane-3-ylideneamino)titanium dichloride.
A transition metal complex of a hydrocarbylamine-substituted heteroaryl compound corresponding to the following formula (VIII) can also be used in the polymerization step.

In formula (VIII), R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms, T ¹ is a divalent crosslinkable group having 1 to 30 atoms other than hydrogen atom, and preferably mono. Or a di-C _1-20 hydrocarbyl substituted methylene or silane group, R ¹⁰ is a C 5-20 heteroaryl group containing Lewis base functionality, preferably pyridin-2-yl or substituted pyridine-2-. An yl group or a divalent derivative thereof, M ¹ is a Group 4 metal, preferably hafnium,
X ¹ is an anionic, neutral or dianionic ligand group, x′ is an integer of 0 to 5, which represents the number of X ¹ groups, and the bond, any bond and electron-contribution interaction are: Represented by a solid line, a broken line and an arrow, respectively.

Examples of the transition metal complex of the hydrocarbylamine-substituted heteroaryl compound represented by the formula (VIII) include formula (IX), formula (X), formula (XI), formula (XII), formula (XIII), and formula The compound represented by (XIV) is mentioned. Among these, the compound represented by the formula (IX) is preferable, the compound represented by the formula (X) is more preferable, and the compound represented by the formula (XI) or the formula (XII) is most preferable.

In formula (IX), M ¹ , X ¹ , x′, R ⁹ and T ¹ are as previously defined and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are not hydrogen, halo or hydrogen. Is an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or silyl group of up to 20 atoms, or adjacent R ¹¹ , R ¹² , R ¹³ or R ¹⁴ groups are bound together, thereby fusing They may form ring derivatives, and bonds, optional bonds and electron pair contributing interactions are represented by solid lines, dashed lines and arrows, respectively.

In formula (X), M ¹ , X ¹ and x′ are as previously defined, R ^a is independently at each _occurrence C _1-4 alkyl, and a is 1-5. And most preferably, R ^a in the two ortho positions to the nitrogen is isopropyl or t-butyl and R ^c is independently at each _occurrence hydrogen, halogen, C _1-20 alkyl or C _{6 -20} aryl, or two adjacent R- ^c groups are joined together, thereby forming a ring, and c is 1-
4 and R ¹⁵ and R ¹⁶ at each occurrence are independently hydrogen, halogen or a C _1-20 alkyl or aryl group, preferably at least one of R ¹⁵ and R ¹⁶ is a group other than hydrogen. , And the bonds, any bonds and electron pair contributing interactions are represented by solid lines, dashed lines and arrows, respectively.

In formula (XI) and formula (XII), M ¹ , X ¹ and x′ are as previously defined, R ¹⁷ and R ¹⁸ are independently at each _occurrence C _1-4 alkyl, or R- ¹⁷ group and R ^{- 18} groups are bonded to each other thereby may form a ring, Ar is C _6-20 aryl group, especially, be a 2-isopropyl phenyl or fused polycyclic aryl group , And the bonds, any bonds and electron pair contributing interactions are represented by solid lines, dashed lines and arrows, respectively.

Particularly preferable transition metal complexes included in the formula (XI) include the following.
[N-(2,6-di(1-methylethyl)phenyl)amide]dimethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amide]dimethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafniumdi(N,N-dimethylamide);
[N-(2,6-di(1-methylethyl)phenyl)amide]dimethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;
[N-(2,6-di(1-methylethyl)phenyl)amide]diethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amide]diethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafniumdi(N,N-dimethylamide);
[N-(2,6-di(1-methylethyl)phenyl)amide]diethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride.

The following are particularly preferable transition metal complexes contained in the formula (XII).
[N-(2,6-di(1-methylethyl)phenyl)amide](o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amide](o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafniumdi(N,N- Dimethylamide);
[N-(2,6-di(1-methylethyl)phenyl)amide](o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride; [N- (2,6-di(1-methylethyl)phenyl)amide](2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amide](2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafniumdi(N,N -Dimethylamide);
[N-(2,6-di(1-methylethyl)phenyl)amide](2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;
[N-(2,6-di(1-methylethyl)phenyl)amide](phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amide](phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafniumdi(N, N-dimethylamide); and [N-(2,6-di(1-methylethyl)phenyl)amide](phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl) Methane)] Hafnium dichloride.

In formula (XIII), M ¹ , X ¹ and x′ are as defined above, R ^a is independently at each _occurrence C _1-4 alkyl, and a is 1-5. And most preferably, R ^a in the two ortho positions to the nitrogen is isopropyl or t-butyl, and R ^c is independently at each _occurrence hydrogen, halogen, C _1-20 alkyl or C _{6 -20} aryl, or two adjacent R- ^c groups are joined together, thereby forming a ring, and c is 1-4, R ¹⁷ and R ¹⁸ are as previously defined. And the bond, any bond and electron pair contributing interaction are represented by a solid line, a broken line and an arrow, respectively.
The most preferred transition metal complex of the above formula is represented by the following formula (XIV).

In formula (XIV), M ¹ is as previously defined and the bond, any bond and electron pair contributing interaction are represented by a solid line, a dashed line and an arrow, respectively.
(Ii) Cocatalyst Each of the above transition metal catalysts (hereinafter referred to as component [D] or “catalyst precursor”) is a known cocatalyst, preferably a cation-forming cocatalyst, a strong Lewis acid, or both of them. 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 [E-1] to [E-4] as a cocatalyst (hereinafter also referred to as component [E]).
Component [E-1]: Organoaluminumoxy compound component [E-2]: Ionic compound component [E-3] capable of reacting with a catalyst precursor and exchanging it with a cation: Lewis acid component [E] E-4]: Layered compound As the organoaluminum oxy compound of the component [E-1], specifically, the following general formula (
Examples thereof include compounds represented by III-1), (III-2), and (III-3).

In each of the above general formulas, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , and R ³⁰ are each independently a hydrogen atom or a hydrocarbon group, It is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms. P represents an integer of 1 to 40, preferably 2 to 30.
The compounds represented by the general formulas (III-1) and (III-2) are organic aluminum oxy compounds (hereinafter sometimes referred to as “aluminoxane”), and one or more kinds of trialkylaluminum and water. It is obtained by the reaction of. Specifically, aluminoxane obtained from one type of trialkylaluminum such as methylaluminoxane and water, or two or more types of alkyl groups obtained from two or more types of trialkylaluminum such as methylethylaluminoxane and water are used. The aluminoxane etc. which it has are mentioned, Methyl aluminoxane, methyl isobutyl aluminoxane, and methyl-n-octyl aluminoxane are more preferable.

It is also possible to use a plurality of kinds of the above organoaluminum oxy compounds in combination. The aluminoxane can be prepared under various known conditions.
The compound represented by the general formula (III-3) is a 10:1 mixture of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the following general formula (III-4). It can be obtained by a reaction of ˜1:1 (molar ratio). In formula (III-4), R ³⁰ represents 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 (}} III-4)
Examples of the ionic compound of the component [E-2] capable of reacting with the component [D] to convert the component [D] into a cation include compounds represented by the following general formula (IV).
[K]e ⁺ [Z]e ⁻ (IV)
In the general formula (IV), 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. In addition, a cation of a metal which is easily reduced by itself, a cation of an organic metal, and the like are also included. Specific examples of the above cations 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 Ions, gold ions, platinum ions, copper ions, palladium ions, mercury ions, ferrocenium ions and the like are included. Triphenyl carbonium, dimethyl octadecyl ammonium, methyl dioctadecyl ammonium, and N,N-dimethylanilinium are preferably used.

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

As the Lewis acid of the component [E-3], particularly as the Lewis acid capable of converting the component [D] into a cation, various triphenylboron, tris(pentafluorophenyl)boron, tris(nonafluorobiphenyl)boron and other organic compounds are used. Examples thereof include boron compounds; metal halogen compounds such as aluminum chloride, magnesium chloride hydride, magnesium bromide hydroxide, and magnesium chloride alkoxide; solid acids such as alumina and silica-alumina; and the like, preferably organic boron compounds, and more preferably Are tris(perfluoroaryl)boron such as tris(pentafluorophenyl)boron and tris(nonafluorobiphenyl)boron.

The layered compound of the component [E-4] is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the contained ions are exchangeable.
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, diatomaceous earth and the like. These may be synthetic products or naturally occurring minerals.
Examples of clay and clay minerals include allophanes such as allophane, kaolinites such as dickite, nacrite, kaolinite, anoxite, halloysites such as metahalloysite, halloysite, chrysotile, lizardite, and antigorite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. smectite, vermiculite, etc. vermiculite minerals, illite, sericite, glaucomite, etc. Examples include clay, gyrome clay, hissingelite, pyrophyllite, and ryokdei stones. These may form a mixed layer.

Examples of artificially synthesized products include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like.
Of these specific examples, preferably kaolin group, halosite group, serpentine group, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, more preferably smectite, vermiculite mineral. , Synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and more preferably montmorillonite.

Examples of the ion-exchangeable layered compound in the component [E-4] include ionic crystalline compounds having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type, and CdI ₂ type. .. Specific examples of the ion-exchange layered compounds having such a crystal _{structure, 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.

Although these [E-4] layered compounds may be used as they are, they are subjected to acid treatment with hydrochloric acid, nitric acid, sulfuric acid, and/or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , It is preferable to perform treatment with a salt such as Ti(SO ₄ ) ₂ , Zr(SO ₄ ) ₂ or Al ₂ (SO ₄ ) ₃ before use. Further, 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 dehydrated and dried before use.
Of the components [E-1] to [E-4], preferably the organoaluminum oxy compound of [E-1], the ionic compound capable of being exchanged with the cation of the component [E-2], and the component [E] -3] Lewis acid is used, and [E-1] organoaluminum oxy compound is particularly preferable.

(Iii) Fine particle carrier In the polymerization step of the present invention, in addition to the above catalyst precursor component [D] and cocatalyst component [E], a fine particle carrier (hereinafter also referred to as component [F]) is allowed to coexist. May be. The component [F] is composed of an inorganic or organic compound, and is a fine particle carrier having a particle diameter of generally 5 μm or more, preferably 10 μm or more, and generally 5 mm or less, preferably 2 mm or less in equivalent circle diameter. Is.

Examples of the inorganic carrier include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ and ZnO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO _{2. 2} , mixed metal oxides such as SiO ₂ —Cr ₂ O ₃ , SiO ₂ —Al ₂ O ₃ —MgO, and the like.
Examples of the organic carrier include (co)polymers of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and aromatic unsaturated compounds such as styrene and divinylbenzene. Examples thereof include fine particle carriers of porous polymers composed of (co)polymers such as hydrocarbons (wherein “(co)polymer” means one or both of “polymer” and “copolymer”). As expected.).

The specific surface area of these fine particle carriers is usually in the range of 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 the above-exemplified various inorganic carriers and/or organic carriers may be used alone, or two or more may be used in any combination and ratio.
In addition to the above-mentioned components [D] and [E] and the above-mentioned optional component [F], the catalyst used in the polymerization step of the present invention is as follows, unless the purpose of the present invention is impaired. Other components such as the component [G] of [1] may be contained.

(Iv) Organoaluminum In the above polymerization step, an organoaluminum compound represented by the following general formula (VII) (hereinafter also referred to as component [G]) may be used as a catalyst.
AlR ³¹ _m X _3-m (VII)
In the general formula (VII), 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.

Specific examples of the preferred organoaluminum compound of the component [G] include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or halogen or alkoxy such as diethylaluminum monochloride and diethylaluminum ethoxide. Including alkyl aluminum. You may mix and use these. Of these, trialkylaluminum, dialkylaluminum alkoxide, or alkylaluminum dialkoxide is particularly preferable. You may use these arbitrary components in combination of 2 or more type.

The catalyst precursor [D] component, the cocatalyst [E] component, and optionally the fine particle carrier [F] component and the organoaluminum [G] component are brought into contact with each other to form an active catalyst composition. Not limited. This contact is preferably carried out not only when the catalyst is prepared but also when the composition of the present invention is produced, by mixing and coordination polymerizing the above-mentioned components (a) to (d) or (a') to (d). You may perform in a process. The contact may be carried out in an inert gas such as nitrogen, during the polymerization reaction described below, or in a solvent. When the solvent is used, it is preferable to use an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene.

The contact temperature is between −20° C. and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent. The molar ratio of [D] component/[E] 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 [E-1] is used as the component [E], it is used in an amount of at least 50 times the amount of the component [D] on a molar basis. When the component [E-2] or the component [E-3] other than the solid Lewis acid is used as the component [E], the molar ratio to the component [D] is usually 0.5 to 10, It is preferably 1 to 6, most preferably 1 to 5.

When the solid Lewis acid in [E-3] or the [E-4] component is used as the [E] component, the [D] component is usually 0.0001 to 10 mmol, preferably 0. It is used at 001-5 mmol. Further, the component [G] is optionally used in the range of 0 to 10000 mmol, preferably 0.01 to 100 mmol.

(V) Polymerization reaction In the polymerization step in the production method of the present invention, the conditions are not particularly limited as long as the intended product is obtained, but preferably the crystalline polypropylene macromonomer, ethylene and α-olefin are simultaneously added to the above catalyst. (When an active catalyst composition is used, the composition is the same. The same applies hereinafter). More preferred is a method in which ethylene and α-olefin and a crystalline polypropylene macromonomer are mixed in advance and the catalyst is brought into contact therewith. More preferably, it is preferable that the polypropylene macromonomer is brought into contact with the catalyst in a molten state or in a state of being substantially dissolved in the monomer or the solvent. The crystalline polypropylene macromonomer may be added all at once before the polymerization, or may be added sequentially or continuously during the polymerization. Further, the step of producing a crystalline polypropylene macromonomer and the step of producing a composition of the present invention by copolymerizing the crystalline polypropylene macromonomer with another olefin monomer can be continuously performed.

At this time, the total addition amount of the crystalline polypropylene macromonomer is not particularly limited, as a result of the polymerization step, in the composition of the present invention obtained, the crystalline polypropylene macromonomer, and the crystalline polypropylene macromonomer. The total amount of the components derived from the monomers is adjusted to 30% by mass or more, preferably 40% by mass or more, and more preferably 45% by mass or more. The component derived from the macromonomer means a partial structure derived from the crystalline polypropylene macromonomer, which constitutes the side chain of the branched structure olefin-based copolymer described above as the component (A).

When the total amount of the crystalline polypropylene macromonomer added is less than the lower limit value described above, the number of copolymer chains substantially including side chains is small, and physical crosslinking between polymer chains tends to be difficult to form. The upper limit of the total amount of the crystalline polypropylene macromonomer added is not limited as long as it does not impair the performance of the composition of the present invention, but is usually preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably Is 75% by mass or less. If the upper limit is exceeded, the flexibility of the entire composition tends to be poor.

After the polymerization step, the crystalline polypropylene macromonomer is incorporated in the composition of the present invention as the side chain component of the branched structure olefin-based copolymer described above as the component (A), and the component (C). Is present in the form of any of the unreacted macromonomers described above. That is, in the composition of the present invention, the crystalline polypropylene macromonomer, and the total weight ratio of the components derived from the macromonomer is the total addition amount of the crystalline polypropylene macromonomer in the production step, specifically Is the same as the weight ratio of the charged weight of the crystalline polypropylene macromonomer expressed as the component (a) or the component (a′) to the obtained elastomer composition.

A solvent may or may not be used in the reaction for producing the composition of the present invention, but it is preferable to use a solvent capable of dissolving the macromonomer during the polymerization reaction. When a solvent is used, examples thereof include hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, benzene, toluene, xylene, cyclohexane, methylcyclohexane and dimethylcyclohexane, chloroform. , 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. Of these, hydrocarbons are preferable. It should be noted that any one of these solvents may be used alone, or two or more of them may be used in any combination and ratio. When these solvents are used, the solvent is usually removed after the reaction by using a known method, and thus is not usually contained in the composition of the present invention. A very small amount of solvent may remain as long as the physical properties are not impaired.

The composition of the present invention can be produced by solution polymerization using the above solvent or slurry polymerization, and liquid phase solventless polymerization, gas phase polymerization or melt polymerization which does not substantially use a solvent can also be used. The polymerization system may be either continuous polymerization or batchwise polymerization. So-called multistage polymerization in which conditions are changed in multiple stages may be adopted. The catalyst concentration is not particularly limited, but when the reaction system is solution polymerization, for example, the content of the component [D] is usually 0.01 mg or more, preferably 0.05 mg or more, and more preferably 0.1 mg with respect to 1 L of the reaction solution. The above range is usually 10 g or less, preferably 1 g or less, and more preferably 0.5 g or less.

The polymerization temperature, the polymerization pressure, and the polymerization time are not particularly limited, but usually, the optimum setting can be performed from the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually in the range of -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. Is. The polymerization pressure is usually 0.01 MPa or higher, preferably 0.05 MPa or higher, more preferably 0.1 MPa or higher, and usually 100 MPa or lower, preferably 20 MPa or lower, more preferably 5 MPa or lower.

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, and It is preferably in the range of 15 hours or less.
In the above polymerization, a molecular weight (MFR) modifier may be used so that the branched structure olefinic copolymer produced has appropriate fluidity. To adjust the molecular weight, a method of regenerating the catalytically active species by moving the polymer chain generated on the catalyst to another atom during the polymerization and replacing it with another atom is used. The agent is called a chain transfer agent. As the chain transfer agent, organoaluminum compounds, organozinc compounds, hydrogen, etc., which are components [D], are preferable in that they do not adversely affect the polymerization activity in general, and hydrogen is particularly preferable in that they are less likely to remain in the product.

[(Component 2) oil]
Examples of the oil include aromatic oils, mineral oils (mineral oils), naphthene oils, paraffin oils, triglyceride vegetable oils such as castor oil, synthetic hydrocarbon oils such as polypropylene oil, and silicone oils.
As the oil, a hydrocarbon-based softening agent for rubber is preferable. Among them, a mineral oil-based or synthetic resin-based softening agent is preferable, a mineral oil-based softening agent is more preferable, and a colorless mineral oil is particularly preferable because of its high affinity for the component 1.

Mineral oil-based softeners are generally mixtures of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons. As the mineral oil-based softening agent, paraffin oil (50% or more of all carbon atoms is paraffin hydrocarbon), naphthenic oil (30 to 45% or more of all carbon atoms is naphthene hydrocarbon) ), and carbon atom aromatic oils (those in which 35% or more of all carbon atoms are aromatic hydrocarbons) are preferable. Among these, it is more preferable to use paraffin oil because it has a good hue.

Examples of the synthetic resin softening agent include polybutene and low molecular weight polybutadiene.
The kinematic viscosity of oil at 40° C. is preferably low from the viewpoint of moldability, but is preferably high from the viewpoint of hygiene of eluted fine particles and the like. Specifically, it is preferably 20 centistokes or more, more preferably 50 centistokes or more, while it is preferably 800 centistokes or less, and more preferably 600 centistokes or less.

The flash point (COC method) of the oil is not limited, but it is preferably 200° C. or higher, and more preferably 250° C. or higher.
The oils may be used alone or in combination of two or more.
In the thermoplastic elastomer composition of the present invention, oil is usually 20 to 250 parts by weight, preferably 50 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the (component 1) elastomer composition. More preferably, it is added in an amount of 50 to 100 parts by weight. When the content is within the above range, the melt fluidity during molding of the thermoplastic elastomer composition, the flexibility of the molded article, and the low temperature characteristics can be improved, and the effect of suppressing stickiness due to bleeding on the surface of the molded article can be obtained. ..

[(Component 3) Filler]
The filler is not particularly limited, and various fillers shown below can be used. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir shell, and bran, and modified products thereof. Further, as the inorganic filler, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite and carbon fibers. Any one of the fillers may be used alone, or two or more thereof may be used in combination.

In the thermoplastic elastomer composition of the present invention, the filler is usually added in an amount of 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the (component 1) elastomer composition. When the content is within the above range, melt flowability during molding of the thermoplastic elastomer composition, flexibility of the molded product, heat resistance, and mechanical strength can be improved, and further, stickiness due to bleeding on the surface of the molded product is suppressed. The effect is obtained.

[(Component 4) Polyolefin]
Specific examples of the polyolefin include polyethylene homopolymers (low-density polyethylene homopolymer, high-density polyethylene homopolymer, etc.), ethylene/α-olefin copolymers, propylene homopolymers, propylene/ethylene copolymers, Propylene/1-butene copolymer, propylene/ethylene/1-butene copolymer, propylene/4-methylpentene copolymer, ethylene-methacrylic acid copolymer and the like and these polymers are modified with an acid anhydride, Those to which a polar functional group is added are included. Among these, polyethylene homopolymer and propylene resin are preferable. Here, the propylene-based resin means a polymer obtained from a monomer mainly containing propylene, specifically, a propylene homopolymer, a propylene/1-butene copolymer, a propylene/ethylene/1-butene copolymer. Are preferred. Among them, propylene homopolymer is particularly desirable. The polyolefin-based resin may be any one of the above-mentioned various polyolefin-based resins, or may be a mixture of a plurality of types. For example, a combination of polyethylene and polypropylene may be used.

The polyolefin resin preferably has a high melt flow rate (MFR) at 230° C. and a load of 2.16 kg measured in accordance with JIS K7210 (1999) test condition 4 in terms of moldability, and is low in terms of mechanical strength. Is preferred. Specifically, the MFR of the polyolefin resin at 230° C. under a load of 2.16 kg is preferably 0.1 g/10 min or more, more preferably 1 g/10 min or more, while 50 g/min.
It is preferably 10 min or less, more preferably 30 g/10 min or less.

In the thermoplastic elastomer composition of the present invention, the polyolefin is usually added in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the (component 1) elastomer composition. When the content is within the above range, the melt fluidity during molding of the thermoplastic elastomer composition, the flexibility of the molded product, and the mechanical strength can be improved.

[Other ingredients]
In the thermoplastic elastomer composition of the present invention, additives other than the above-mentioned components 1 to 4 may be used as long as the effects of the present invention are not significantly impaired. With specific additives, various heat stabilizers, antioxidants, ultraviolet absorbers, antiaging agents, plasticizers, light stabilizers, crystal nucleating agents, impact modifiers, pigments, lubricants, antistatic agents, Examples include flame retardants, flame retardant aids, compatibilizers, tackifiers and the like. Only one kind of these additives and the like may be used, or two or more kinds thereof may be used in an optional combination and ratio.

Examples of the heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.
The flame retardant is roughly classified into a halogen-based flame retardant and a non-halogen flame retardant, and the non-halogen flame retardant is preferable in terms of environment. As non-halide flame retardants, phosphorus-based flame retardants, hydrated metal compounds (aluminum hydroxide, magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine-based, guanidine-based) flame retardants and inorganic-based compounds (molybdenum compounds) Examples include a flame retardant and the like.

[Method for producing thermoplastic elastomer composition]
The method for obtaining the thermoplastic elastomer composition in the present invention is not particularly limited as long as the raw material components are uniformly dispersed. That is, a resin composition in which each component is uniformly distributed can be obtained by mixing the above-mentioned respective raw material components and the like at the same time or in any order.
The thermoplastic elastomer composition of the present invention includes a state in which the raw material components are dry blended as they are, and for more uniform mixing/dispersion, the raw material components are melt-mixed to obtain a resin composition. It is preferable to set. As a method of melt mixing, for example, each raw material component of the resin composition in the present invention may be mixed in any order and then heated, or all raw material components may be sequentially melted and mixed, or each raw material may be mixed. The mixture of the components and the like may be pelletized or melt-mixed at the time of molding when the target molded article is manufactured.

There is no particular limitation on the mixing method and the mixing conditions when the above-mentioned raw material components are mixed, as long as the raw material components are uniformly mixed, but from the viewpoint of productivity, a single-screw extruder or a twin-screw extruder is used. A known melt-kneading method such as a continuous kneader as described above and a batch-type kneader such as a mill roll, a Banbury mixer (registered trademark), a Labo Plastomill (registered trademark), and a pressure kneader is preferable. The temperature at the time of melt mixing may be a temperature at which at least one of the raw material components is in a molten state, but a temperature at which all the components used are usually selected, and generally 150 to 250° C. ..

[Physical Properties of Thermoplastic Elastomer Composition]
The thermoplastic elastomer composition of the present invention has high heat resistance at 100°C. The reason is that the branched structure olefin-based copolymer contained in the component 1 has a comb structure of main chain (soft segment)-side chain (hard segment), so that the crystal part of the side chain is 100° C. or higher. It is considered that the property as a constraint point of physical crosslinking is maintained even at a high temperature. The thermoplastic elastomer composition of the present invention preferably has a compression set of 90% or less measured at 120° C. according to JIS K6262.

[Uses of thermoplastic elastomer composition]
Since the thermoplastic elastomer composition (oil-extended composition) of the present invention is excellent in fluidity and heat resistance, soft PVC and thermoplastic elastomer are used in addition to conventional ethylene-based materials and propylene-based materials. In various fields, it can be suitably used as a simple substance, as a main component, or as an additive.

The molding method of the thermoplastic elastomer composition of the present invention and the resin composition (modified product) containing the thermoplastic elastomer composition of the present invention is not particularly limited, but in the film/sheet, an inflation method applied to polyolefin, 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. When laminating, the extrusion laminating method, the thermal laminating method, the dry laminating method and the like are possible, and the film can be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, a tubular method and the like. Further, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment and the like which are usually used industrially can be applied.

When a laminate is formed by taking advantage of the excellent fluidity and heat resistance of the thermoplastic elastomer composition of the present invention, the material for forming the other layers includes propylene homopolymer and propylene/α-olefin copolymer. , Various propylene-based polymers such as 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 copolymers, various olefin-based copolymers such as polybutene-1, poly-4-methylpentene-1 (TPX resin), and adhesive polyolefins modified with maleic anhydride, etc. , Polyamide, polyester, polyester elastomer, and the like.

(Use 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 the following uses can be given as an example.
That is, a stretch film for packaging, a commercial or household wrap film, a pallet stretch film, a stretch label, a shrink film, a shrink label, a sealant film, a retort film, a retort sealant film, a heat-welding film, a heat-bonding film, a heat Sealing film, bag-in-box sealant film, retort pouch, standing pouch, spout pouch, laminated tube, heavy bag, textile packaging film, etc. Film field, infusion bag, multi-chamber container for high calorie infusion and peritoneal dialysis (CAPD), drainage bag for peritoneal dialysis, blood bag, urine bag, surgical bag, ice pillow, ampoule case, PTP packaging, etc. Medical film/sheet field, civil engineering water-blocking sheet, waterproofing material, jointing material, flooring, roofing, decorative film, skin film, wallpaper and other building material related fields, leather, ceiling material, trunk room lining, interior skin material, Automotive parts field such as vibration control sheets, sound insulation sheets, display covers, battery cases, mouse pads, mobile phone cases, IC card cases, CD-ROM cases, etc., low-electricity fields, toothbrush cases, puff cases, cosmetic cases, drug cases such as eye drops Toiletries or sanitary fields such as tissue cases, face packs, film/sheets for stationery, clear files, pen cases, notebook covers, desk mats, keyboard covers, book covers, binders and other office supplies related fields, furniture leather, beach Toys such as balls, umbrellas, rain gear such as raincoats, table cloths, blister packages, bath covers, towel cases, fancy cases, tag cases, pouches, amulets, insurance cards covers, passbook cases, passport cases, cutlery cases, etc. General household use, miscellaneous goods, retroreflective sheeting, synthetic paper, etc. Further, as a film/sheet field in which an adhesive material is applied to a base material to give adhesiveness, adhesive tapes, marking films, dicing films for semiconductors or glasses, surface protective films, steel sheet/plywood protective films, automobile protective films , Packing/bundling adhesive tape, office/household adhesive tape, joining adhesive tape, paint masking adhesive tape, surface protection adhesive tape, sealing adhesive tape, anticorrosion/waterproof adhesive tape, electrical insulation adhesive tape, Examples include adhesive tapes for electronic devices, adhesive films, adhesive tapes for medical/sanitary materials such as Bansoukou base film, adhesive tapes for identification/decoration, display tapes, packaging tapes, surgical tapes, and adhesive tapes for labels.

(Use in the field of injection molding and extrusion molding)
The use of the thermoplastic elastomer composition of the present invention or its modified product in the fields of injection molding and extrusion molding is not particularly limited, but the following uses can be mentioned as an example. That is, coating materials for electric wires, cords, wire harnesses, etc. in the field of electric and electronic parts, insulating sheets, control cable covering materials for automobile parts, airbag covers, mudguards, bumpers, boots, air hoses, lamp packings, gaskets. , Various kinds of malls such as window moldings, site shields, weather strips, glass run channels, grommets, vibration control/sound insulation materials, home appliances, various packings in the field of low-electricity, grips, belts, rubber feet, rollers, protectors, suckers , Gaskets for refrigerators, various rolls for OA equipment, tubular molded products such as hoses, tubes, extruded products, leather-like articles, engaging devices, toys such as dolls with soft touch, pen grips, toothbrush patterns General goods such as etc., containers such as houseware, tapperware, binding bands, infusion bottles by blow molding, bottles for food, bottles for personal care such as cosmetics, catheters for medical parts, syringes, syringes Examples thereof include gaskets, drip tubes, tubes, ports, caps, rubber stoppers, disposable containers, and the like, and applications by foam molding are also possible.

(Use 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 field of fibers and non-woven fabrics is not particularly limited, but the following uses can be given as an example. That is, continuous spinning, continuous crimped yarn, short fibers, fibers such as monofilaments, flat yarn, melt blown method, nonwoven fabric by the spunbond method, for sanitary materials such as paper diapers, surgical clothes, medical items such as gloves, Applications include carpets, their linings, and ropes. Further, knitted materials such as these non-woven fabrics, monofilaments, flat yarns, slit tapes, etc., and canvas, tent materials, hoods, flexible containers, leisure sheets, tarpaulins, etc. obtained by laminating films/sheets can be mentioned.

(Use in modifier)
INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention or a modified product thereof has excellent affinity with polypropylene, and therefore can be suitably used for modifying polypropylene. The modification improves not only flexibility, transparency, toughness, etc., but also heat sealability, impact resistance, and affinity with additives, and can be used for improving the surface of a molded product. In addition, hot melt adhesives, tackifiers, asphalt modification, bitumen modification, waterproof paper, and the like that take advantage of their heat fusion properties are also mentioned as examples of applications.

(Other uses)
The thermoplastic elastomer compositions in the present invention can be used to make durable products for the automotive, building, medical, food and beverage, electrical, electrical appliances, office machines and consumer markets. In some embodiments, the thermoplastic elastomer composition is used in toys, grips, soft-touch grips, bumper lab strips, flooring, automatic door mats, handles, casters, furniture and appliance legs, tags. , Seals, gaskets such as static and dynamic gaskets, automobile doors, bumper fascias, grill components, rocker panels, hoses, backings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, Used to make flexible durable parts or articles selected from plunger tips, delivery systems, kitchen utensils, shoes, shoe praders and soles. In other embodiments, the thermoplastic elastomer composition can be used to make durable parts or articles that require high tensile strength and low compression set. In a further embodiment, the thermoplastic elastomer composition can be used to make durable parts or articles that require high maximum service temperature and low modulus.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In addition, the measurement of physical properties, analysis and the like in the following examples are according to the following methods.
(1) GPC measurement The weight average molecular weight (Mw) of the thermoplastic elastomer composition was determined by GPC measurement. The GPC measurement was performed by using Alliance GPCV2000 manufactured by Waters and using a differential refractometer as a detector. As the column, four Tosoh TSKgel GMH6-HTs were used.

Ortho-dichlorobenzene was used as the mobile phase solvent, and it was allowed to flow out at 135° C. and 1.0 mL/min. As a standard sample, Polymer Laboratories monodisperse polystyrene is used, a calibration curve for retention time and molecular weight is prepared from the viscosity formulas of the polystyrene standard sample and the ethylene polymer, and the molecular weight of the molecular weight is calculated based on the calibration curve. Calculation was performed. As the viscosity formula, [η]=K×M ^α is used, for polystyrene, K=1.38×10 ⁻⁴ , α=0.70 is used, and for the ethylene polymer, As for K, 4.77×10 ⁻⁴ and α=0.70 were used.

Regarding the number average molecular weight ([Mn(GPC)]) of the crystalline polypropylene macromonomer, monodisperse polystyrene manufactured by Polymer Laboratories was used as a standard sample, and the polystyrene standard sample and the propylene polymer were used. A calibration curve for retention time and molecular weight was prepared from the viscosity formula, and the molecular weight was calculated based on the calibration curve. As the viscosity formula, [η]=K×M ^α is used, K=1.38×10 ⁻⁴ and α=0.70 are used for polystyrene, and propylene polymer is used. , K=1.03×10 ⁻⁴ and α=0.78 were used.

(2) DSC measurement The melting point (Tm) of the polymer, the crystallization temperature (Tc), and the glass transition point (Tg) were measured by DSC measurement. For DSC measurement, "Diamond DSC" manufactured by PerkinElmer is used, isothermal at 20° C. for 1 minute, temperature increase from 20 to 210° C. at 10° C./minute, isothermal at 210° C. for 5 minutes, 210 to −10 at 10° C./minute. The temperature was lowered to 70° C., isothermal at −70° C. for 5 minutes, and then measured at a temperature rise of −70 to 210° C. at 10° C./min.

(3) NMR measurement The number average molecular weight ([Mn/NMR]) of the crystalline propylene macromonomer containing a vinyl group at one end was measured by ¹ H-NMR spectrum, and one end of all macromonomer molecules was labeled with vinyl. It was calculated from the total number of protons of the alkyl group when it was assumed to be a group. The stereoregularity (isotactic pentad fraction) of the macromonomer was determined by measuring the ¹³ C-NMR spectrum of the polymer. <NMR measurement conditions>
The solvent used was a 1,2-dichlorobenzene/deuterobromobenzene (4/1) mixed solvent. The sample concentration was 50-250 mg/2.4 mL, and after introducing into the NMR sample tube, the atmosphere was sufficiently replaced with nitrogen and then dissolved in a heat block at 130° C. to obtain a uniform solution. The measurement was performed at 130° C. using a BrukerAvanceIIICryo-NMR and a 10 mmφ cryoprobe.

The measurement conditions are as follows: ¹ H-NMR: solvent presaturation method, 18° pulse, total 256 times, ¹³ C-NMR: proton complete decoupling condition, 90° pulse, total 512 times.
The chemical shift reference peak was determined by using the signal of the methyl group of hexamethyldisiloxane added to the measurement solvent, and was set to 0.08 ppm in ¹ H NMR and 1.979 ppm in ¹³ C NMR.

<Method of calculating isotactic pentad (mmmm) fraction>
The isotactic pentad (mmmm) fraction of the polypropylene macromonomer was determined from the ¹³ C-NMR measurement result based on the following calculation formula. For attribution of the described pentad mmmm, mrrm and triad mm, reference was made to the literature (Chem. Rev. 2000, 100, 1253-1345).
mmmm fraction=(I _mm −2×I _mrrm )/(I _mm +3×I _mrrm )
I _mm : integrated intensity of signal of 23.0-21.2 ppm derived from isotactic triad mm I _mrrm : integrated intensity of signal of 19.9 to 19.7 ppm derived from pentad mrrm

<Calculation method of ethylene content of polymer main chain>
The ethylene content of the polymer main chain was determined by the following formula, which is the ratio of the ethylene content (wt%) of the entire polymer to the weight derived from the polymer main chain in the polymer. The ethylene content of the entire polymer was determined by the method described in the literature (Macromolecules 2006, 39, 8223-8228).
Main chain ethylene content (wt%)
= 100 x (ethylene content of the entire polymer)/(100-macromonomer content)
The main chain ethylene content (mol%) was calculated from the main chain ethylene content (wt%).

(4) Macromonomer Content in Thermoplastic Elastomer The amount of macromonomer contained in the thermoplastic elastomer was determined from the weight percentage of the macromonomer charged at the time of polymerization with respect to the weight of the obtained composition.

(5) Melt flow rate (MFR)
According to the test condition 4 of JIS K7210 (1999), the measured value at 230° C. under a load of 2.16 kg was obtained.

(Production Example 1)
[Synthesis of rac-dimethylsilylenebis(2-(2-(5-methyl)-furyl)-4-(4-isopropylphenyl)phenyl-indenyl)hafnium dichloride (hereinafter, "complex M1")]
Complex M1 was synthesized according to the method described in Production Example M-1 of WO 2008/059969.

(Production Example 2)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer A)]
Purified hexane (10000 mL) and a toluene solution of modified methylaluminoxane (Tosoh Finechem Co., Ltd. “MMAO-3A” 2.1 mmol [Al equivalent) Atom]) was introduced in an amount of 60 mL. The reaction vessel was heated to 85° C., propylene was introduced to 0.80 MPa, and the toluene solution of the complex M1 (43.7 μmol) obtained in Production Example 1 was pressure-inserted into the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to maintain the reactor pressure at 0.80 MPa. 8
After 0 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 2211 g of polymer. The number average molecular weight ([Mn(GPC)]) of the obtained macromonomer is 10900, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR is 0.908, and the terminal vinyl ratio. Was 94%. The melting point (Tm) and the crystallization temperature (Tc) measured by DSC were 138° C. and 110° C., respectively.

(Production Example 3)
[Synthesis of rac-dimethylsilylenebis(2-(2-(5-methyl)-furyl)-4-(4-isopropylphenyl)phenyl-indenyl)zirconium dichloride (hereinafter, "complex M2")]
The complex M2 was synthesized according to the method described in JP-A 2004-2259.

(Production Example 4)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer B)]
Purified hexane (1000 mL) and a toluene solution of modified methylaluminoxane (Tosoh Finechem Co., Ltd. “MMAO-3A” 2.1 mmol [converted into Al] were placed in an induction stirring autoclave with an internal volume of 2 L, which was replaced with purified nitrogen and had a stirring blade. Atom]) was introduced in an amount of 4 mL. The reaction vessel was heated to 70° C., propylene was introduced to 0.20 MPa, and the toluene solution of the complex M2 (5.0 μmol) obtained in Production Example 3 was pressure-inserted into the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to keep the reactor pressure at 0.20 MPa. After 60 minutes, ethanol was introduced to stop the reaction. The obtained polymer was collected by filtration and dried under reduced pressure until the amount became constant to obtain 210 g of polymer. The number average molecular weight ([Mn(GPC)]) of the obtained macromonomer was 26000, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.975, and the terminal vinyl ratio. Was 83%. The melting point (Tm) and the crystallization temperature (Tc) measured by DSC were 150° C. and 118° C., respectively.

(Production Example 5)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer C)]
Purified hexane (1000 mL) and a toluene solution of modified methylaluminoxane (Tosoh Finechem Co., Ltd. “MMAO-3A” 2.1 mmol [converted into Al] were placed in an induction stirring autoclave with an internal volume of 2 L, which was replaced with purified nitrogen and had a stirring blade. Atom]) was introduced in an amount of 4 mL. The reaction vessel was heated to 70° C., propylene was introduced to 0.40 MPa, and the toluene solution of the complex M2 (2.0 μmol) obtained in Production Example 3 was pressure fed to the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to maintain the reactor pressure at 0.40 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 fixed amount was obtained to obtain 250 g of a polymer. The number average molecular weight ([Mn(GPC)]) of the obtained macromonomer was 38000, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.984, and the terminal vinyl ratio was obtained. Was 73%. The melting point (Tm) and the crystallization temperature (Tc) measured by DSC were 155°C and 119°C, respectively.

(Production Example 6)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer D)]
1 mL of purified propylene (1250 mL) and a toluene solution of triisobutylaluminum (0.5 mol/L [Atomic equivalent atom]), which was replaced with purified nitrogen, was introduced into an induction stirring autoclave with an internal volume of 2 L and a stirring blade. did. The reaction vessel was heated to 75° C., propylene was saturated at 3.4 MPa, and the complex M1 (6.0 μmol) obtained in Production Example 1 was added to Production Example M-1 of WO 2008/059969. The toluene slurry solution (4 mL) prepared according to the method described was pressure-fed to the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to maintain the reactor pressure at 3.40 MPa. After 60 minutes, propylene was degassed from the system to stop the reaction. The obtained polymer was collected by filtration and dried under reduced pressure until the amount became constant to obtain 382 g of polymer. The number average molecular weight ([Mn(GPC)]) of the obtained macromonomer was 65000, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.972, and the terminal vinyl ratio was obtained. Was 97%. The melting point (Tm) and the crystallization temperature (Tc) measured by DSC were 154° C. and 117° C., respectively.

(Production Example 7)
[Production of Isotactic Polypropylene Macromonomer (Macromonomer E)]
Purified hexane (10000 mL) and a toluene solution of modified methylaluminoxane (Tosoh Finechem Co., Ltd. “MMAO-3A” 2.1 mmol [converted into Al] were placed in an induction stirring autoclave with an internal volume of 24 L, which was replaced with purified nitrogen and contained a stirring blade. Atom]) was introduced in an amount of 40 mL. The reaction vessel was heated to 70° C., propylene was introduced to 0.40 MPa, and the toluene solution of the complex M2 (20.0 μmol) obtained in Production Example 3 was pressure-inserted into the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to maintain the reactor pressure at 0.40 MPa. After 70 minutes, ethanol was introduced to stop the reaction. The obtained polymer was collected by filtration and dried under reduced pressure until the amount became constant, to obtain 2253 g of polymer. The number average molecular weight ([Mn(GPC)]) of the obtained macromonomer was 27,000, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.978, and the terminal vinyl ratio was obtained. Was 82%. The melting point (Tm) and the crystallization temperature (Tc) measured by DSC were 154° C. and 111° C., respectively.
Table 1 shows the physical property values of the macromonomers produced in Production Examples 2 to 7.

(Production Example 8)
[Synthesis of dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl (complex C1)]
Complex C1 was synthesized according to the method described in Example UT of US Pat. No. 6,265,338.

(Production Example 9)
The polypropylene macromonomer A (120.0 g) obtained in Production Example 2 and the modified methylaluminoxane (“MMAO-Tosoh Finechem Co., Ltd.” in an induction stirring autoclave with an internal volume of 24 L, which was replaced with purified nitrogen and contained a stirring blade, were used. 3A” 18.5 mmol [atomic equivalent of Al]), BHT (2,6-di-tert-butyl-p-cresol, 313.5 mg), and dry toluene (4600 mL) were introduced. The reactor was heated to 95°C, stirred for 15 minutes and then cooled to 70°C. After keeping the reactor at 70° C. and introducing a mixed gas of propylene and ethylene (propylene/ethylene=35/65 molar ratio) into the polymerization tank up to 0.40 MPa, the complex C1 (26.6 μmol) obtained in Production Example 8 was introduced. The toluene solution of () was introduced at a rate of 13 mL/min to start the reaction. During the reaction, a mixed gas was added to maintain the pressure of the reactor 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 poured into ethanol to precipitate the polymer. The obtained polymer was separated by filtration, the polymer collected by filtration was further washed with ethanol, and dried under reduced pressure until a fixed amount was obtained to obtain 387 g of a polymer (thermoplastic elastomer composition). The physical properties of the resulting thermoplastic elastomer composition are shown in Table 2.

(Production Example 10)
[Synthesis of (N-2,6-diisopropylphenylamide)dimethyl(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane))hafnium dimethyl (complex C2)]
The complex C2 was synthesized according to the method described in WO 2008/112133, Working Example 4. The structural formula of the complex C2 is shown by the following formula (W1).

(Production Example 11)
The polypropylene macromonomer A (120.0 g) obtained in Production Example 2 and the modified methylaluminoxane (“MMAO-Tosoh Finechem Co., Ltd.” in an induction stirring autoclave with an internal volume of 24 L, which was replaced with purified nitrogen and contained a stirring blade, were used. 3A” 18.5 mmol [atomic equivalent of Al]), BHT (313.5 mg), and dry toluene (4600 mL) were introduced. The reactor was heated to 95°C, stirred for 15 minutes and then cooled to 70°C. The reactor was heated to 95°C, stirred for 15 minutes and then cooled to 70°C. After keeping the reactor at 70° C. and introducing a mixed gas of propylene and ethylene (propylene/ethylene=35/65 molar ratio) into the polymerization tank up to 0.40 MPa, the complex C2 (18.4 μmol) obtained in Production Example 10 was introduced. The toluene solution of () was introduced at a rate of 13 mL/min to start the reaction. During the reaction, a mixed gas was added to maintain the pressure of the reactor 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 poured 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 the amount became constant to obtain 215 g of a polymer (thermoplastic elastomer composition). The physical properties of the resulting thermoplastic elastomer composition are shown in Table 2.

(Production Example 12)
Polymerization was performed in the same manner as in Production Example 11 except that Macromonomer B was used instead of Macromonomer A as a macromonomer, to obtain 249 g of a polymer.

(Production Example 13)
Polymerization was carried out in the same manner as in Production Example 11 except that Macromonomer C was used instead of Macromonomer A as a macromonomer to obtain 195 g of a polymer.

(Production Example 14)
Polymerization was performed in the same manner as in Production Example 13 except that the amount of catalyst was doubled (53.2 μmol) and the polymerization time was extended to 120 minutes to obtain 233 g of a polymer.

(Production Example 15)
The polypropylene macromonomer A (2.00 kg) obtained in Example 2, 1-octene (10.0 L), and triisobutylaluminum were placed in an autoclave having an internal volume of 1000 L and having an anchor type stirring blade, which was replaced with purified nitrogen. A 1:1 mixture of BHT/BHT (4.60 mmol [atomic equivalent of Al]) and dry toluene (230 L) were introduced. The reactor was heated to 100° C. and stirred for 10 minutes, after which the reactor was cooled to 70° C. Ethylene was added until the reactor pressure was 0.2 MPa. On the other hand, dry toluene (32 L) was introduced into the catalyst tank, and a 1:1 mixture of triisobutylaluminum/BHT (4.60 mmol [atomic equivalent of Al]), complex C2 (13.3 mmol) and trispentafluorophenylborane (13). .9 mmol) was introduced and dissolved. The catalyst solution was started to be pressed in with a diaphragm pump (injection rate: 40 L/hour) to start the reaction. During the reaction, ethylene was added to maintain the pressure of the reactor at 0.2 MPa, and the pressure injection rate of the catalyst was changed between 0 and 40 L/h to control the heat generation by the reaction. When the amount of ethylene absorbed reached about 6 kg, ethanol was introduced to stop the reaction. From the remaining amount of the catalyst tank, the total amount of the complex C2 used was 8.46 mmol. The gas in the reactor was released, and the reaction solution was poured into methanol to precipitate the polymer. The polymer solution collected by filtration was washed with acetone and dried under reduced pressure until a fixed amount was obtained to obtain 14.6 kg of a polymer.

(Production Example 16)
Polymerization was performed in the same manner as in Production Example 9 except that Macromonomer D was used instead of Macromonomer A as a macromonomer to obtain 393 g of a polymer.

(Production Example 17)
Polymerization was carried out in the same manner as in Production Example 9 except that macromonomer E was used as the macromonomer instead of macromonomer A and the composition of the mixed gas of propylene and ethylene was propylene/ethylene=20/80 molar ratio. Conducted to obtain 342 g of polymer.

(Production Example 18)
Polymerization was performed in the same manner as in Production Example 11 except that the macromonomer was not added, to obtain 98 g of a polymer.

(Production Example 19)
In a 1 L four-necked separable flask, 12.5 g of the polymer obtained in Production Example 18 , 12.5 g of the polypropylene macromonomer E obtained in Production Example 7, and 500 mL of xylene were added,
After heating and stirring at 130° C. for 2 hours and confirming that the solution was uniform, the mixture was allowed to cool to 50° C. Acetone (300 mL) was added dropwise using a dropping funnel, and the mixture was stirred at 50° C. for 1 hour. After cooling to room temperature, the precipitated polymer was filtered off and the filtered polymer was further washed with acetone and heated to 70°C.
After drying for 6 hours under reduced pressure, 25 g of polymer was recovered.

(Production Example 20)
Polymerization was performed in the same manner as in Production Example 13 except that the macromonomer was not added to obtain 255 g of a polymer.

(Production Example 21)
In a 1 L four-necked separable flask, 21.1 g of the polymer obtained in Production Example 20 , 10.4 g of the polypropylene macromonomer E obtained in Production Example 7, and 500 mL of xylene were added,
After heating and stirring at 130° C. for 1 hour and confirming that the solution was uniform, the solution was allowed to cool to 50° C. The obtained solution was poured into acetone to precipitate the polymer. The precipitated polymer was separated by filtration, and the collected polymer was washed with acetone and dried under reduced pressure at 70° C. for 6 hours to give 31 g.
Was recovered.
The following raw materials were used in the examples and comparative examples of the present invention. In addition, the component 1 used in the present invention
The details are shown in Table 2.

<Component 2>
"Diana Process Oil PW-90" manufactured by Idemitsu Kosan Co., Ltd.: Paraffin-based process oil

<Component 3>
"Novatech PP MA1Q" manufactured by Japan Polypropylene Corporation: polypropylene homopolymer. MFR (230° C., 2.16 kg) 22 g/10 minutes. Tm 161°C.

<Production of oil-extended composition>
An R60 mixer (internal volume 60 cc) and a “Labo Plastomill” manufactured by Toyo Seiki Seisaku-sho, Ltd. equipped with a roller type blade were used for the melt kneading. Based on the blending ratio (weight ratio) shown in Table 3, the polymer of the production example, PW-90 and MA1Q were made to have a total of 42 g, and IRGANOX1010 manufactured by BASF Co., Irgafos168 manufactured by BASF Co., and calcium stearate 42 mg each. In addition, the mixture was melt-kneaded at 180 rpm for 10 minutes to obtain an oil-extended composition.

<Evaluation of oil-extended composition>
(Compression set)
According to JIS K6262 (2006), a test piece with a diameter of 29 mm obtained by punching three 2.0 mm thick sheets obtained by press molding at 200° C. was compressed with a dedicated jig. Then, heat treatment was performed in a gear oven maintained at 70°C or 120°C. After 22 hours, the test piece was taken out from the dedicated jig, released from compression, and the recovery rate of its thickness was measured. The results are shown in Table 3.

(Duro A hardness)
Table 3 shows the results of measurement according to JIS K6253 (1993) using the sheet obtained by molding as described above.

From Table 3, it can be seen that the oil extended composition of the thermoplastic elastomer of the present invention has both heat resistance and fluidity. More specifically, the compositions of Examples had both a low compression set value and a flowable MFR value at a high temperature of 70° C. or higher.
As is clear from Examples 4 to 6, even when the amount of oil to be blended is increased, the fluidity can be greatly improved while maintaining the compression set. Moreover, by comparing Examples 1 to 2 and 8 (using the macromonomer A) and Examples 3 to 7 and 9 to 10 (using one of the macromonomers B to E), a higher melting point (mmmm min. Of the thermoplastic elastomer oil-extended composition prepared using a macromonomer having a lower melting point than the thermoplastic elastomer oil-extended composition prepared using a macromonomer having a lower melting point. It can be seen that at a certain temperature of 120°C, it exhibits an excellent compression set.

On the other hand, in the compositions of Comparative Examples 1 and 2, a mixture of an ethylene/propylene copolymer and a polypropylene macromonomer was used instead of the branched structure olefin-based copolymer of the component 1. In Comparative Example 1, in the production of the oil-extended composition, it was not possible to produce a uniform sample worthy of measuring the compression set. The composition of Comparative Example 2 exhibited fluidity, but had a large compression set value and poor heat resistance.

According to the present invention, it is possible to obtain a thermoplastic elastomer composition having excellent fluidity and heat resistance by oil-extending kneading.

Claims (10)

A thermoplastic elastomer composition comprising the following component 1 and component 2.
(Component 1) having a main chain of an ethylene/α-olefin copolymer and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end, and the α-olefin content in the main chain Is 70 mol% or less, an elastomer composition containing a branched structure olefin-based copolymer.
(Component 2) oil The thermoplastic elastomer composition according to claim 1, further comprising the following component 3 and/or component 4.
(Component 3) Filler (Component 4) Polyolefin The thermoplastic elastomer composition according to claim 1 or 2, wherein the crystalline propylene polymer of the component 1 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 of the component 1 has a number average molecular weight of 50,000 or less. The heat according to any one of claims 1 to 4, wherein Component 1 contains the crystalline propylene polymer and components derived from the crystalline propylene polymer in a total amount of 30% by mass or more and 90% by mass or less. Plastic elastomer composition. The heat according to any one of claims 1 to 5, which contains 50 to 200 parts by weight of oil, 0 to 200 parts by weight of filler, and 0 to 100 parts by weight of polyolefin with respect to 100 parts by weight of the elastomer composition. Plastic elastomer composition. The thermoplastic elastomer composition according to any one of claims 1 to 6, which has a compression set of 90% or less measured at 120°C according to JIS K6262. The thermoplastic elastomer composition according to any one of claims 2 to 7, wherein the polyolefin is polyethylene, polypropylene, or a combination thereof. A molded product obtained by using the composition according to claim 1. The molded product according to claim 9, which is selected from the group consisting of an injection molded product, a thermoformed product, and a calendered product.